CN101134800B - Pigment dispensing composition, optical solidified composition, color filter and manufacturing method thereof - Google Patents

Pigment dispensing composition, optical solidified composition, color filter and manufacturing method thereof Download PDF

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CN101134800B
CN101134800B CN2007101483983A CN200710148398A CN101134800B CN 101134800 B CN101134800 B CN 101134800B CN 2007101483983 A CN2007101483983 A CN 2007101483983A CN 200710148398 A CN200710148398 A CN 200710148398A CN 101134800 B CN101134800 B CN 101134800B
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pigment
acid
methyl
polymkeric substance
composition
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CN101134800A (en
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辻畑茂朝
杉原幸一
高桥秀知
藤牧一广
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Fujifilm Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Abstract

The invention provides a pigment dispersion combination with good pigment dispersilbility and dispersion stability, a photocurable combination, a color filter can get high contrast and a manufacturing method therefor, provides a pigment dispersion combination formed by polymers containing a monomeric copolymerization unit expressed by the formular (1) and pigment in the organic solvent. In the formular (1), R<1> represents H or substituted or unsubstituted alkyl. R<2> represents alkylidene group. W represents -C(=O)O-, -CONH-, phenylene and so on. X represents -S-, -CONH-, -C(=O)S-, -NHCONH-,-NHC(=O)S- and so on. Y represents -NR<3>-, -O-, -S-, or -N=, which is connected with adjacent atom groups or N to form an annular structure. R<3> represents H, alkyl or aryl. m and n represent 0 or 1 respectively.

Description

The manufacture method of pigment dispensing composition, Photocurable composition, colour filter and colour filter
Technical field
The present invention relates to pigment dispensing composition, contain the Photocurable composition of this pigment dispensing composition, the colour filter that uses this Photocurable composition formation and the manufacture method of this colour filter.
Background technology
Photocurable composition contains pigment dispensing composition and polyfunctional monomer, Photoepolymerizationinitiater initiater, alkali soluble resins and other composition that has disperseed pigment dyestuff or mineral dye.Colour filter by with Photocurable composition, utilize the formation colored patterns such as photoetch method to make.
In recent years, colour filter not only is used for indicating meter as the purposes of liquid crystal display device (LCD), also is used for televisor (TV), and purposes is the trend of expansion.The trend of following this purposes to enlarge requires look characteristic highly at aspects such as colourity, contrast gradients.In addition, when being used for image sensor (solid-state imager), require too the high colour filter of look characteristic.
For above-mentioned requirements, need to make with finer state colo(u)rant dispersion (good dispersiveness), disperse (good dispersion stabilization) with stable state.Have following problem when pigment dispersed insufficient: produce flange (edge part spination) and concave-convex surface at formed painted etchant resist, the colourity of the colour filter of manufacturing and dimensional precision descend, and perhaps contrast gradient is significantly deteriorated etc.And when the dispersion stabilization of pigment is insufficient, easily produce following problem: in the manufacturing process of colour filter, particularly, the uniformity decreases of the thickness in the painting process of Photocurable composition, sensitization sensitivity in exposure process descends, perhaps degradation under the alkali dissolution in developing procedure.In addition, when the dispersion stabilization of pigment is poor, also there is following problem: follow the passing of time, the constituent generation aggegation of Photocurable composition, viscosity rise becomes extremely short working life.
But if with the particle diameter miniaturization of pigment, then the surface-area of pigment particles becomes large, and therefore, the cohesive force between pigment particles strengthens, and in most cases is difficult to have simultaneously high-caliber dispersiveness and dispersion stabilization.
In order to overcome the above problems, various pigment dispersing agents have been developed.In these dispersion agents, the multipolymer that comprises macromonomer (oligopolymer that has endways the olefinic unsaturated group) is useful.Disclose: the multipolymer that comprises this macromonomer (oligopolymer that has endways the olefinic unsaturated group) by use carries out dispersion treatment, can obtain the dispersible pigment dispersion that pigment particle size is little, dispersion stabilization is excellent (for example with reference to patent documentation 1,2).
But there is following problem in the multipolymer that comprises macromonomer described in the patent documentation 1,2: because it does not have the functional group that promotes pigment adsorption, so can not play a role as dispersion agent separately, must be used in combination with other dispersion agent.And, when the multipolymer that will comprise such macromonomer uses as the dispersion agent of pigment, although the viscosifying action that can suppress to occur in the macromolecule dispersing agent, because fully not carrying out the miniaturization of pigment, so there is the dispersed inadequate problem of pigment.
Be to improve the dispersion stabilization of pigment, disclose the graftomer of part-structure (for example with reference to patent documentation 3) with organic pigment, nitrogen heterocyclic ring (for example with reference to patent documentation 4), cyclic imide base (for example with reference to patent documentation 5).
But present situation is dispersiveness and the pigment dispensing composition of dispersion stabilization excellence and the Photocurable composition that contains this pigment dispensing composition that pigment also do not occur.
[patent documentation 1] Unexamined Patent 8-259876 communique
[patent documentation 2] Unexamined Patent 10-339949 communique
[patent documentation 3] JP 2003-26950 communique
[patent documentation 4] JP 2003-26949 communique
[patent documentation 5] JP 2003-277673 communique
Summary of the invention
The present invention makes in view of above-mentioned problems of the prior art point, to reach following purpose as problem.
Namely, the object of the present invention is to provide the pigment dispensing composition of dispersiveness and the dispersion stabilization excellence of pigment, and provide the dispersiveness of pigment and dispersion stabilization is excellent, be cured and can form the Photocurable composition of the tunicle of transmitance and contrast gradient excellence by exposure.
Another object of the present invention is to provide the manufacture method of the colour filter that can obtain high-contrast and such colour filter.
People of the present invention have carried out wholwe-hearted research, found that, the polymkeric substance that has ad hoc structure by use can solve above-mentioned problem, thereby finish the present invention as pigment dispersing agent.
That is, as follows for the means that solve above-mentioned problem.
＜1〉pigment dispensing composition, it contains pigment and polymkeric substance and forms in organic solvent, and described polymkeric substance comprises the copolymerization units that comes from by the monomer of following general formula (1) expression.
General formula (1)
Figure S2007101483983D00031
In general formula (1), R 1Expression hydrogen atom or replacement or unsubstituted alkyl.R 2The expression alkylidene group.W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.X represents-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-or-NHCO-.Y represents-NR 3-,-O-,-S-or-N=, it forms ring texture by adjacent with it atomic group and the former sub-connection of N.R 3Expression hydrogen atom, alkyl or aryl.M and n represent 0 or 1 independently of one another.
＜2〉according to above-mentioned＜1〉described pigment dispensing composition, wherein, in above-mentioned general formula (1), Y is the condensed ring structure by the ring texture that adjacent atomic group and the former sub-connection of N form.
＜3〉according to above-mentioned＜1〉or＜2〉described pigment dispensing composition, wherein, described polymkeric substance is the graft copolymer that further comprises the copolymerization units that comes from the polyreactive oligomers that has endways ethylenic unsaturated bond.
＜4〉according to above-mentioned＜1〉or＜2〉described pigment dispensing composition, wherein, described polymkeric substance is the polymkeric substance that further comprises the copolymerization units that comes from the monomer with acidic group.
＜5〉according to above-mentioned＜1〉described pigment dispensing composition, wherein, the acid number of described polymkeric substance is 10～150mgKOH/g.
＜6〉according to above-mentioned＜1〉described pigment dispensing composition, wherein, described pigment is from C.I. pigment yellow 13 9, C.I. Pigment Yellow 73 150, C.I. pigment green 36, C.I. Pigment red 177, C.I. Pigment red 254, C.I. pigment Blue 15: 6 and the group that forms of C.I. pigment Violet 23 at least a pigment selected.
＜7〉Photocurable composition, it contains above-mentioned＜1〉described pigment dispensing composition, optical polymerism compound and Photoepolymerizationinitiater initiater.
＜8〉according to above-mentioned＜7〉described Photocurable composition, it also contains alkali soluble resins.
＜9〉according to above-mentioned＜7〉or＜8〉described Photocurable composition, wherein, described Photoepolymerizationinitiater initiater is from triazine based compound, lophine (2,4,5-triphenyl imidazoles) at least a Photoepolymerizationinitiater initiater of selecting in the group that dipolymer class based compound and oxime compound form.
＜10〉according to above-mentioned＜7〉or＜8〉described Photocurable composition, it is used for colour filter.
＜11〉colour filter, its have at substrate use above-mentioned＜10 colored pattern that forms of described Photocurable composition.
＜12〉manufacture method of colour filter, it comprises following operation: photosensitive film forms operation, and it is with above-mentioned＜10〉described Photocurable composition is applied directly on the substrate or across other layer and is applied on the substrate, thus the formation photosensitive film; Colored pattern forms operation, and it is by formed photosensitive film being carried out successively pattern exposure and develop to form colored pattern.
According to the present invention, can provide to have high pigment-dispersing and the pigment dispensing composition of dispersion stabilization, the Photocurable composition that the dispersiveness of pigment and dispersion stabilization are excellent, be cured and can form the tunicle of transmitance and contrast gradient excellence by exposure can also be provided.
In addition, according to the present invention, can also provide the manufacture method of the colour filter that can obtain high-contrast and such colour filter.
Embodiment
Below, be elaborated for the manufacture method of pigment dispensing composition of the present invention, Photocurable composition, colour filter and colour filter.
＜pigment dispensing composition 〉
Pigment dispensing composition of the present invention is the polymkeric substance that contains pigment and comprise the copolymerization units that comes from the monomer that is represented by following general formula (1) in organic solvent.
(polymkeric substance that comprises the copolymerization units that comes from the monomer that is represented by general formula (1))
Pigment dispensing composition of the present invention need to contain the polymkeric substance that comprises the copolymerization units that comes from the monomer that is represented by following general formula (1).
In pigment dispensing composition of the present invention, polymkeric substance is the material that can play a role as pigment dispersing agent.In the following description, sometimes suitably will " comprise the polymkeric substance that comes from by the copolymerization units of the monomer of general formula (1) expression " and be called " specific pigment dispersion agent " and describe.
General formula (1)
Figure S2007101483983D00051
In general formula (1), R 1Expression hydrogen atom or replacement or unsubstituted alkyl.R 2The expression alkylidene group.W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.X represents-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-or-NHCO-.Y represents-NR 3-,-O-,-S-or-N=, it forms ring texture by adjacent with it atomic group and the former sub-connection of N.R 3Expression hydrogen atom, alkyl or aryl.M and n represent 0 or 1 independently of one another.
Below, be elaborated for the monomer by general formula (1) expression of copolymerization units essential in the specific pigment dispersion agent that forms as important component of the present invention.
In general formula (1), R 1Expression hydrogen atom or replacement or unsubstituted alkyl.
As by R 1The alkyl of expression, preferred carbonatoms is 1～12 alkyl, and more preferably carbonatoms is 1～8 alkyl, and particularly preferably carbonatoms is 1～4 alkyl.
When by R 1When the alkyl of expression is substituted alkyl, as the substituting group that can import, such as listing: hydroxyl, alkoxyl group, aryloxy, acyloxy, halogen radical etc.
As by R 1The preferred alkyl of expression specifically can list: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-methoxy ethyl etc.
As R 1, particularly preferably hydrogen atom or carbonatoms are 1～4 alkyl.
R 2The expression alkylidene group.
As by R 2The alkylidene group of expression, preferred carbonatoms is 1～12 alkylidene group, and more preferably carbonatoms is 1～8 alkylidene group, and particularly preferably carbonatoms is 1～4 alkylidene group.
About by R 2The alkylidene group of expression in the situation that can import, also can have substituting group, as this substituting group, such as listing: hydroxyl, alkoxyl group, aryloxy, acyloxy etc.
As by R 2The preferred alkylidene group of expression specifically can list methylene radical, ethylidene, propylidene, trimethylene, tetramethylene etc.
W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene, preferred-C (=O) O-,-CONH-or phenylene.
Y represents-NR 3-,-O-,-S-or-N=, it forms ring texture by adjacent with it atomic group and the former sub-connection of N.
R 3Expression hydrogen atom, alkyl or aryl.As by R 3The alkyl of expression can preferably list carbonatoms and be 1～12 alkyl etc., as by R 3The aryl of expression can preferably list phenyl, naphthyl etc.
R 3More preferably hydrogen atom or carbonatoms are 1～4 alkyl, are particularly preferably hydrogen atom or methyl.
As Y, particularly preferably-S-,-NH-or-N=.
The ring texture that forms by adjacent with it atomic group and the former sub-connection of N as Y, can list the single ring architectures such as imidazole ring, pyrimidine ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, and the condensed ring structure such as benzoglyoxaline ring, benzothiazole ring, benzoxazole ring, purine skeleton, quinazoline ring, perimidine, from with the viewpoint of the affinity of pigment, preferred condensed ring structure.In the condensed ring structure, particularly preferably benzoglyoxaline ring, benzothiazole ring and benzoxazole ring.
X represents-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-or-NHCO-.As X, particularly preferably-O-,-S-,-CONH-,-NHCONH-and-NHC (=O) S-.
M and n represent 0 or 1 independently of one another, and particularly preferably m and n are 1.
The below lists the preferred object lesson (monomer M-1～monomer M-18) by the monomer of general formula (1) expression, but the invention is not restricted to these.
Figure S2007101483983D00081
From the viewpoint of the dispersion stabilization of giving pigment, specific pigment dispersion agent of the present invention is preferably to contain and comes from by the copolymerization units of the monomer of above-mentioned general formula (1) expression, further contains the graft copolymer of the copolymerization units that comes from the polyreactive oligomers that has endways ethylenic unsaturated bond simultaneously.
The polyreactive oligomers that has endways ethylenic unsaturated bond like this is the compound with molecular weight of regulation because of it, so be also referred to as macromonomer.In the following description, sometimes suitably " polyreactive oligomers that has endways ethylenic unsaturated bond " among the present invention is called " polyreactive oligomers " or " macromonomer ".
In the present invention, consist of according to the polymerisable functional moieties with ethylenical unsaturated double bonds of the required polyreactive oligomers that uses by polymer chain part and its end.From obtaining the viewpoint of needed graftomer, such group with ethylenical unsaturated double bonds preferably exists only in an end of polymer chain.As the group with ethylenical unsaturated double bonds, preferred (methyl) acryl, vinyl, particularly preferably (methyl) acryl.
In addition, the number-average molecular weight in polystyrene conversion of this macromonomer (Mn) is preferably in 1000～10000 scope, the scope particularly preferably in 2000～9000.
In general, homopolymer or multipolymer that the part of above-mentioned polymer chain is formed by at least a monomer of selecting the group that forms from (methyl) alkyl acrylate, Styrene and its derivatives, vinyl cyanide, vinyl-acetic ester and divinyl, or polyoxyethylene, polyoxypropylene, polycaprolactone.
Above-mentioned polyreactive oligomers is preferably by the oligopolymer shown in the following general formula (2).
General formula (2)
Figure S2007101483983D00091
In the general formula (2), R 11And R 13Represent independently respectively hydrogen atom or methyl.
R 12Expression contains the connection base that carbonatoms is 1～12 alkylidene group, and this connection base can be that carbonatoms is 1～12 alkylidene group, also can be the connection base that a plurality of these alkylidene groups are formed by connecting by ester bond, ehter bond, amido linkage etc.As R 12, preferred carbonatoms is 1～4 alkylidene group, or carbonatoms is the group that 1～4 alkylidene group is formed by connecting by ester bond.By R 12The alkylidene group of expression can also have substituting group (for example hydroxyl).
Y represents not have substituent phenyl, have phenyl that 1 carbonatoms is 1～4 alkyl or-COOR 14The R here 14The expression carbonatoms is that 1～6 alkyl, phenyl or carbonatoms are 7～10 aralkyl.Y be preferably phenyl or-COOR 14, but the R here 14The expression carbonatoms is 1～12 alkyl.
Q represents 20～200 integer.
In the present invention; preferred example as the synthetic polyreactive oligomers (macromonomer) that can be used for the specific pigment dispersion agent can list: poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate and poly-(methyl) isobutyl acrylate, connected (methyl) acryl and the polymkeric substance that obtains at an end of polystyrene molecule.As the above-mentioned polyreactive oligomers that can obtain from market, can list: single end has carried out the polystyrene oligomer (Mn=6000 of methacrylic acidylate; trade(brand)name: AS-6; East Asia synthetic chemical industry Co., Ltd. system); single end has carried out the polymethyl methacrylate oligomer (Mn=6000 of methacrylic acidylate; trade(brand)name: AA-6; East Asia synthetic chemical industry Co., Ltd. system) and single end carried out the positive butyl ester oligopolymer of the polyacrylic acid (Mn=6000 of methacrylic acidylate; trade(brand)name: AB-6; East Asia synthetic chemical industry Co., Ltd. system).
Specific pigment dispersion agent of the present invention preferably further comprises the copolymerization units that comes from the monomer with acidic group.The specific pigment dispersion agent is by further comprising the copolymerization units that comes from the monomer with acidic group, thereby when for example pigment dispensing composition of the present invention being applicable to form pattern by photoetch method, can further improve the pattern formative.
As the monomer with acidic group, can list: the unsaturated monocarboxylic acid classes such as vinylformic acid, methacrylic acid, butenoic acid, α-chloroacrylic acid, styracin; Unsaturated dicarboxylic acid or its anhydrides such as toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid, itaconic anhydride, citraconic acid, citraconic anhydride, methylfumaric acid; Unsaturated polycarboxylic acid or its anhydrides that ternary is above; List ((methyl) acryloyloxyalkyl) the ester class of the polycarboxylic acid that the binary such as mono succinate (2-acrylyl oxy-ethyl) ester, mono succinate (2-methylacryoyloxyethyl) ester, phthalic acid list (2-acrylyl oxy-ethyl) ester, phthalic acid list (2-methylacryoyloxyethyl) ester are above; List (methyl) esters of acrylic acid of the two terminal carboxyl(group) polymkeric substance such as ω-carboxyl-polycaprolactone single-acrylate, ω-carboxyl-polycaprolactone monomethacrylates etc.
Specific pigment dispersion agent of the present invention can also further contain copolymerizable vinyl monomer as the copolymerization composition in the scope that does not affect its effect.
As at this operable vinyl monomer, be not particularly limited such as the ester class of preferred (methyl) esters of acrylic acid, crotonate class, vinyl ester, maleic acid diester class, dimethyl ester class, methylene-succinic acid diester class, (methyl) acrylic amide, vinyl ethers, vinyl alcohol, styrenic, (methyl) vinyl cyanide etc.As the object lesson of such vinyl monomer, for example can list following compound.
As the example of (methyl) esters of acrylic acid, can list: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid tertiary butyl cyclohexyl, (methyl) 2-EHA, (methyl) vinylformic acid uncle monooctyl ester, (methyl) dodecylacrylate, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid acetoxyl group ethyl ester, (methyl) phenyl acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-(2-methoxy ethoxy) ethyl ester, (methyl) vinylformic acid 3-phenoxy group-2-hydroxy propyl ester, (methyl) benzyl acrylate, diethylene glycol monomethyl ether (methyl) acrylate, diethylene glycol monoethyl ether (methyl) acrylate, triethylene glycol monomethyl ether (methyl) acrylate, triglycol list ether (methyl) acrylate, poly glycol monomethyl ether (methyl) acrylate, polyethyleneglycol ether (methyl) acrylate, (methyl) vinylformic acid beta-phenoxy ethoxy ethyl ester, Nonylphenoxy polyoxyethylene glycol (methyl) acrylate, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) vinylformic acid two cyclopentenes oxygen base ethyl esters, (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid octafluoro amyl group ester, (methyl) vinylformic acid perfluoro capryl ethyl ester, (methyl) vinylformic acid two ring pentyl esters, (methyl) tribromophenyl acrylate, (methyl) vinylformic acid tribromophenoxy ethyl ester etc.
In addition, in this manual expression in " propenyl, methylpropenyl " any one party or during both sides, sometimes be denoted as " (methyl) propenyl ".
As the example of crotonate class, can list butyl crotonate and the own ester of butenoic acid etc.
As the example of vinyl ester, can list vinyl-acetic ester, propionate, vinyl butyrate, methoxyacetic acid vinyl acetate and M-nitro benzoic acid vinyl acetate etc.
As the example of maleic acid diester class, can list dimethyl maleate, ethyl maleate and dibutyl maleinate etc.
As the example of dimethyl ester class, can list dimethyl fumarate, DEF and dibutyl fumarate etc.As the example of methylene-succinic acid diester class, can list dimethyl itaconate, diethyl itaconate and dibutyl itaconate etc.
As (methyl) acrylic amide, can list (methyl) acrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-propyl group (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N-normal-butyl (methyl) acrylamide, the N-tertiary butyl (methyl) acrylamide, N-cyclohexyl (methyl) acrylamide, N-(2-methoxy ethyl) (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N-phenyl (methyl) acrylamide, N-benzyl (methyl) acrylamide, (methyl) acryloyl morpholine, diacetone-acryloamide(DAA) etc.
As the example of styrenic, can list vinylbenzene, vinyl toluene, dimethyl styrene, Three methyl Benzene ethene, ethyl styrene, isopropyl benzene ethene, butylstyrene, hydroxy styrenes, methoxy styrene, butyl phenyl ether ethene, acetoxy-styrene, chloro-styrene, dichlorostyrene, bromstyrol, 1-chloro-4-methyl-benzene, by hydroxy styrenes, vinyl M-nitro benzoic acid methyl esters and the alpha-methyl styrene etc. of the de-protected group of available acidic substance (such as t-Boc etc.) protection.
As the example of vinyl ethers, can list methylvinylether, butyl vinyl ether, hexyl vinyl ether and methoxy ethyl vinyl ether etc.
The acid number of the specific pigment dispersion agent among the present invention is preferably 10～150mgKOH/g, and more preferably 20～140mgKOH/g is particularly preferably 30～120mgKOH/g.
If the acid number of specific pigment dispersion agent is in the scope of 10～150mgKOH/g, when then pigment dispensing composition of the present invention being applicable to resist liquid, the alkali dissolution of resist liquid is kept aptly, has realized good development, and pigment has been realized excellent dispersion stabilization simultaneously.
Maintain method in the above-mentioned optimum range as the acid number with the specific pigment dispersion agent, such as enumerating the method that contains the copolymerization composition with acidic group 1% or more in the polymkeric substance that consists of the specific pigment dispersion agent of sening as an envoy to or the polymkeric substance that makes formation specific pigment dispersion agent by high molecular weight reactive such as with the method for acid anhydrides addition etc.
Here, the acid number of specific pigment dispersion agent refers to, the mg number of the needed potassium hydroxide of this pigment dispersing agent 1g that neutralizes.The unit of acid number is mgKOH/g.Acid number can be obtained the point of neutralization by with alkaline solution (for example aqueous sodium hydroxide solution, potassium hydroxide aqueous solution) solution of resin being carried out titration, calculates according to the amount that arrives alkaline solution required till this point of neutralization.During titration, obtain the point of neutralization such as volumetry that can be by having used the titrate indicators such as phenolphthalein or with the method for automatic electric potential difference titration apparatus.
As the preferred configuration of specific pigment dispersion agent of the present invention, can preferably list and contain coming from by the copolymerization units of the monomer of above-mentioned general formula (1) expression, further containing the copolymerization units that comes from the polyreactive oligomers that has endways ethylenic unsaturated bond of 10～90 quality %, the copolymerization units that comes from the monomer with acidic group of 1～30 quality %, the multipolymer that 0～20 quality % comes from the copolymerization units of vinyl monomer of 2～50 quality %.
About the preferred molecular weight of specific pigment dispersion agent of the present invention, preferably count 15000～200000, count 8000～100000 with number-average molecular weight (Mn) with weight-average molecular weight (Mw).In addition, molecular weight can be measured by GPC.
Below, list object lesson (exemplary compounds 1～exemplary compounds 16) and weight-average molecular weight thereof applicable to the specific pigment dispersion agent of pigment dispensing composition of the present invention, but the invention is not restricted to these.
Exemplary compounds (1): above-mentioned monomer M-2/ end has carried out polymethyl methacrylate copolymer (10/90 quality %, weight-average molecular weight 50000, the acid number: 0mgKOH/g) of methacrylic acidylate
Exemplary compounds (2): above-mentioned monomer M-2/ methacrylic acid/end has carried out polymethyl methacrylate copolymer (10/15/75 quality %, weight-average molecular weight 30000, the acid number: 98mgKOH/g) of methacrylic acidylate
Exemplary compounds (3): above-mentioned monomer M-3/ 2-hydroxyethyl methacrylate/end has carried out polymethyl methacrylate copolymer (5/10/85 quality %, weight-average molecular weight 40000, the acid number: 0mgKOH/g) of methacrylic acidylate
Exemplary compounds (4): above-mentioned monomer M-3/ methacrylic acid/benzyl methacrylate multipolymer/end has carried out polymethyl methacrylate copolymer (15/5/10/65 quality %, weight-average molecular weight 60000, the acid number: 33mgKOH/g) of methacrylic acidylate
Exemplary compounds (5): above-mentioned monomer M-4/ end has carried out polymethyl methacrylate copolymer (10/90 quality %, weight-average molecular weight 80000, the acid number: 0mgKOH/g) of methacrylic acidylate
Exemplary compounds (6): above-mentioned monomer M-4/ methacrylic acid/end has carried out polymethyl methacrylate copolymer (10/15/75 quality %, weight-average molecular weight 30000, the acid number: 98mgKOH/g) of methacrylic acidylate
Exemplary compounds (7): above-mentioned monomer M-5/ vinylformic acid/end has carried out polymethyl methacrylate copolymer (25/15/60 quality %, weight-average molecular weight 60000, the acid number: 117mgKOH/g) of methacrylic acidylate
Exemplary compounds (8): above-mentioned monomer M-5/ end has carried out butyl polyacrylate multipolymer (15/85 quality %, weight-average molecular weight 40000, the acid number: 0mgKOH/g) of methacrylic acidylate
Exemplary compounds (9): above-mentioned monomer M-6/ 2-hydroxyethyl methacrylate/end has carried out polymethyl methacrylate copolymer (15/10/75 quality %, weight-average molecular weight 80000, the acid number: 0mgKOH/g) of methacrylic acidylate
Exemplary compounds (10): above-mentioned monomer M-6/ end has carried out polymethyl methacrylate copolymer (12/88 quality %, weight-average molecular weight 50000, the acid number: 0mgKOH/g) of methacrylic acidylate
Exemplary compounds (11): above-mentioned monomer M-7/ methacrylic acid/end has carried out polymethyl methacrylate copolymer (10/15/75 quality %, weight-average molecular weight 25000, the acid number: 98mgKOH/g) of methacrylic acidylate
Exemplary compounds (12): above-mentioned monomer M-7/ methacrylic acid/benzyl methacrylate/methoxy polyethylene glycol methacrylate-styrene polymer multipolymer (10/10/50/30 quality %, weight-average molecular weight 40000, acid number: 65mgKOH/g)
Exemplary compounds (13): above-mentioned monomer M-10/ 2-hydroxyethyl methacrylate/end has carried out polystyrene copolymer (5/10/85 quality %, weight-average molecular weight 20000, the acid number: 0mgKOH/g) of methacrylic acidylate
Exemplary compounds (14): above-mentioned monomer M-10/ methacrylic acid/end has carried out polymethylmethacrylate (10/15/75 quality %, weight-average molecular weight 35000, the acid number: 98mgKOH/g) of methacrylic acidylate
Exemplary compounds (15): above-mentioned monomer M-10/ methoxy polyethylene glycol methacrylate-styrene polymer multipolymer (15/85 quality %, weight-average molecular weight 15000, acid number: 0mgKOH/g)
Exemplary compounds (16): above-mentioned monomer M-13/ methacrylic acid/end has carried out polymethyl methacrylate copolymer (10/15/75 quality %, weight-average molecular weight 20000, the acid number: 98mgKOH/g) of methacrylic acidylate
Exemplary compounds (17): above-mentioned monomer M-4/ methacrylic acid/end has carried out polymethyl methacrylate copolymer (10/15/75 quality %, weight-average molecular weight 25000, the acid number: 98mgKOH/g) of methacrylic acidylate
Exemplary compounds (18): above-mentioned monomer M-4/ vinylformic acid/end has carried out polystyrene copolymer (10/10/80 quality %, weight-average molecular weight 20000, the acid number: 78mgKOH/g) of methacrylic acidylate
Exemplary compounds (19): the succinyl oxide affixture/end of above-mentioned monomer M-4/ 2-hydroxyethyl methacrylate has carried out polymethyl methacrylate copolymer (8/15/77 quality %, weight-average molecular weight 25000, the acid number: 37mgKOH/g) of methacrylic acidylate
Exemplary compounds (20): above-mentioned monomer M-4/ vinylformic acid/benzyl methacrylate/end has carried out polymethyl methacrylate copolymer (10/10/10/70 quality %, weight-average molecular weight 25000, the acid number: 78mgKOH/g) of methacrylic acidylate
Exemplary compounds (21): above-mentioned monomer M-10/ vinylformic acid/end has carried out polymethyl methacrylate copolymer (15/10/75 quality %, weight-average molecular weight 25000, the acid number: 78mgKOH/g) of methacrylic acidylate
Exemplary compounds (22): above-mentioned monomer M-11/ methacrylic acid/end has carried out polymethyl methacrylate copolymer (15/10/75 quality %, weight-average molecular weight 25000, the acid number: 65mgKOH/g) of methacrylic acidylate
Exemplary compounds (23): above-mentioned monomer M-11/ end has carried out polymethyl methacrylate copolymer (15/85 quality %, weight-average molecular weight 30000, the acid number: 0mgKOH/g) of methacrylic acidylate
Can be by making by the monomer of above-mentioned general formula (1) expression, in solvent, carrying out the incompatible acquisition of radical polymerization according to the required polyreactive oligomers that is used in combination or other monomer as the above-mentioned multipolymer of the specific pigment dispersion agent among the present invention.As radical polymerization initiator, can use known compound, the preferred azo series initiators (for example 2 that uses, two (2 Methylpropionic acid) dimethyl esters of 2 '-azo, azobisisobutyronitrile, 2, two (2-amidine propane) dihydrochlorides of 2 '-azo) etc.), superoxide (benzoyl peroxide, Potassium Persulphate etc.).Except initiator, can also further add chain-transfer agent (for example 2 mercapto ethanol, 3-thiohydracrylic acid, 2-Thiovanic acid, dodecyl mercaptans) and come synthetic.
In addition, will be described later about concrete synthetic example.
The content of specific pigment dispersion agent in pigment dispensing composition is 0.5～100 quality % with respect to the quality optimization of aftermentioned pigment, more preferably 3～70 quality %.If the amount of pigment dispersing agent in this scope, then can obtain sufficient colo(u)rant dispersion effect.In addition, even adding can not obtain better colo(u)rant dispersion effect sometimes more than the pigment dispersing agent of 100 quality %.
Pigment dispensing composition of the present invention contains pigment and specific pigment dispersion agent and forms in organic solvent, also can use as required other one-tenth such as resinous principle to assign to consist of.
Because this pigment dispensing composition contains the specific pigment dispersion agent, so the dispersion state of pigment is good in the organic solvent, can obtain good look characteristic, meanwhile, for example when consisting of colour filter, also can obtain high-contrast.Particularly in pigment dyestuff, bring into play excellent dispersion effect.
(pigment)
Pigment dispensing composition of the present invention contains pigment, and as this pigment, choice for use in the past known various mineral dye or pigment dyestuff can suit.
No matter pigment is mineral dye or pigment dyestuff, is preferred words if consider high-transmission rate, then preferably uses the size of particles little pigment of trying one's best.If also consider operability, then the median size of pigment is preferably 0.01 μ m～0.1 μ m, more preferably 0.01 μ m～0.05 μ m.
As above-mentioned mineral dye, can list the metallic compound with expressions such as metal oxide, metallic complex salts.Particularly, can enumerate tap a blast furnace, the metal oxide of cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony etc. and composite oxides of above-mentioned metal etc.
As above-mentioned pigment dyestuff, for example can list following material.
C.I. Pigment Yellow 73 11,24, and 31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C.I. pigment orange 36,38,43,71;
C.I. pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;
C.I. pigment violet 19,23, and 32,37,39;
C.I. pigment blue 1,2,15,15:1,15:3,15:6,16,22,60,66;
C.I. pigment Green 7,36,37;
C.I. pigment brown 25,28;
C.I. Pigment black 1,7;
Pigment as among the present invention is not particularly limited, but more preferably following pigment.
C.I. Pigment Yellow 73 11,24, and 108,109,110,138,139,150,151,154,167,180,185;
C.I. pigment orange 36,71;
C.I. pigment red 122,150,171,175,177,209,224,242,254,255,264;
C.I. pigment violet 19,23, and 37;
C.I. pigment Blue 15: 1,15:3,15:6,16,22,60,66;
C.I. pigment green 36;
C.I. Pigment black 7.
Wherein, following pigment particularly preferably.
C.I. pigment yellow 13 9,150;
C.I. Pigment red 177,254;
C.I. pigment Violet 23;
C.I. pigment Blue 15: 6;
C.I. pigment green 36;
These pigment dyestuffs can use separately, or carry out various being used in combination in order to improve purity of color.The object lesson of combination is as follows.
For example, as red pigment, can use separately anthraquione pigmentss, perylene pigments, diketopyrrolopyrrolecocrystals series pigments or general's at least a and tetrazo wherein is that yellow ultramarine, isoindoline are that yellow ultramarine, quinophthalone are that yellow ultramarine Huo perylene is that red pigment is mixed use etc.For example, as anthraquione pigmentss, can list C.I. Pigment red 177 Zuo is perylene pigments, C.I. Pigment red 155, C.I. Pigment red 224 can be listed, as the diketopyrrolopyrrolecocrystals series pigments, C.I. Pigment red 254 can be listed, consider from the color reproduction aspect, preferably mix with C.I. Pigment Yellow 73 1 39.In addition, the mass ratio of red pigment and yellow ultramarine is preferred 100: 5～100: 50.When mass ratio is lower than 100: 5, sometimes be difficult to suppress the optical transmittance of 400nm～500nm, can't improve purity of color.And when mass ratio surpassed 100: 50, predominant wavelength became near the short wavelength sometimes, became large with departing from of NTSC target tone.Especially, the optimum scope of above-mentioned mass ratio is 100: 10～100: 30.And, when red pigment combination with one another, can adjust according to colourity.
In addition, as veridian, can use separately the halo phthualocyanine pigment, or be that yellow ultramarine, quinophthalone are that yellow ultramarine, azomethine are that yellow ultramarine or isoindoline are that yellow ultramarine mixes use with itself and tetrazo.For example, as such example, preferred C.I. pigment Green 7,36,37 mixes with C.I. pigment yellow 83, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. Pigment Yellow 73 150, C.I. Pigment Yellow 73 180 or C.I. Pigment Yellow 73 185.Preferred 100: 5～100: 150 of the mass ratio of veridian and yellow ultramarine.When mass ratio is lower than 100: 5, sometimes is difficult to suppress the optical transmittance of 400nm～450nm, and can't improves purity of color.And when mass ratio surpassed 100: 150, predominant wavelength became near the long wavelength sometimes, became large with departing from of NTSC target tone.Particularly preferably 100: 30～100: 120 scope of mass ratio.
As blue pigments, can use separately phthualocyanine pigment, or be that violet pigment mixes use with itself Yu dioxazine.For example, preferred C.I. pigment Blue 15: 6 mix with the C.I. pigment Violet 23.Preferred 100: 0～100: 50 of the mass ratio of blue pigments and violet pigment, more preferably 100: 5～100: 30.
In addition, as black matrix" pigment, can use separately or mix use that carbon, titanium are black, ferric oxide, titanium oxide, the combination of preferred carbon and titanium carbon.And, preferred 100: 0～100: 60 scope of mass ratio that carbon and titanium are black.When surpassing 100: 60, dispersion stabilization descends sometimes.
The content of pigment is preferably 40～90 quality % with respect to the total solids composition (quality) of said composition in the pigment dispensing composition, more preferably 50～80 quality %.When the content of pigment was in above-mentioned scope, depth of shade fully and can effectively guarantee excellent look characteristic.
(organic solvent)
The organic solvent that uses during as modulation pigment dispensing composition of the present invention can list: 2-acetoxyl group-1-methoxy propane, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethyl acetate, butylacetate, ethyl lactate, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone, n-propyl alcohol, 2-propyl alcohol, propyl carbinol, hexalin, ethylene glycol, glycol ether, toluene, dimethylbenzene etc.
In addition, the addition of organic solvent is selected aptly according to purposes of pigment dispensing composition etc.But, when being used for the modulation of aftermentioned Photocurable composition, from the viewpoint of operability, can being added into the solid component concentration that contains pigment and pigment dispersing agent and reaching 5～50 quality %.
The modulation of pigment dispensing composition of the present invention is not particularly limited, for example, can be with pigment, pigment dispersing agent and solvent with vertical or horizontal sand mill, needle mill, slit shredder, ultrasonic dispersing machine etc., carry out loose processing of differential with the bead of being made by glass, zirconium white etc. of 0.01～1mm particle diameter and obtain.
And, carry out before bead disperses, can carry out with twin-roll machine, three-roller, ball mill, trommel, dispersion machine, kneader, when the forcing machine etc. of kneader, clarifixator, blending machine, single screw rod or twin screw is given stronger shearing force altogether mixing dispersion treatment.
In addition, on the books in T.C.Patton work " Paint Flow andPigment Dispersion " (John Wiley and Sons company periodical in 1964) etc. about mixing, the details that disperses.
Pigment dispensing composition of the present invention can also be applicable to inkjet, ink etc. except being applicable to form colour filter.
In addition, when pigment dispensing composition of the present invention is used to form colour filter, in the preferred alkaline soluble aqueous solution.
＜Photocurable composition 〉
Photocurable composition of the present invention contains above-mentioned pigment dispensing composition of the present invention, optical polymerism compound and Photoepolymerizationinitiater initiater, preferably further contains alkali soluble resins, as required, can also contain other composition.
Because this Photocurable composition contains above-mentioned specific pigment dispersion agent of the present invention, therefore, pigment keeps good dispersion state in composition, can obtain good look characteristic, meanwhile, for example when consisting of colour filter, can obtain high-contrast.
Below, be elaborated for each composition that contains in the Photocurable composition of the present invention.
(pigment dispensing composition)
Photocurable composition of the present invention is to adopt at least a in the above-mentioned pigment dispensing composition of the present invention and consist of.About the details of the pigment dispensing composition of the present invention that consists of Photocurable composition, as mentioned above.
Content as the pigment dispensing composition in the Photocurable composition of the present invention, the content of preferred pigments is with respect to the total solids composition (quality) of the Photocurable composition amount in the scope of 5～70 quality %, more preferably in the amount of the scope of 15～60 quality %.When the content of pigment dispensing composition was in above-mentioned scope, depth of shade fully and can effectively guarantee excellent look characteristic.
(alkali soluble resins)
Photocurable composition of the present invention preferably contains at least a alkali soluble resins.Photocurable composition is by containing alkali soluble resins, thereby when this Photocurable composition is applicable to form pattern by photoetch method, can further improve the pattern formative.
As alkali soluble resins, can be from being to contain at least one alkali soluble resins that promotes alkali-soluble group (such as carboxyl, phosphate, sulfonic group etc.) wire organic high molecular polymer and the molecule (the preferably molecule take propenyl based copolymer, styrene based copolymer as main chain) to select aptly.Wherein, the alkali soluble resins that further preferably solvable and available weak base aqueous solution develops in organic solvent.
About the manufacturing of alkali soluble resins, for example, can be suitable for the method for utilizing known radical polymerization to carry out.The polymerizing conditions such as kind of the kind of the temperature when making alkali soluble resins with radical polymerization, pressure, radical initiator and consumption thereof, solvent to those skilled in the art, can easily be set, and also can experimentally impose a condition.
As above-mentioned wire organic high molecular polymer, preferably has the polymkeric substance of carboxylic acid at side chain.For example; can list JP 59-44615 number; examined patent publication 54-34327 number; examined patent publication 58-12577 number; examined patent publication 54-25957 number; JP 59-53836 number; the Sipacril 2739OF of putting down in writing in JP 59-71048 number each communique; acrylic copolymer; itaconic acid copolymer; the butenoic acid multipolymer; maleic acid; partial esterification maleic acid etc.; and the acid cellulose derivative that has carboxylic acid at side chain; have the polymkeric substance of hydroxyl and the adduct of acid anhydrides etc., can also preferably list the high molecular polymer that has (methyl) acryl at side chain.
(methyl) benzyl acrylate/(methyl) acrylic copolymer or by multiple copolymer that (methyl) benzyl acrylate/(methyl) vinylformic acid/other monomer forms wherein, particularly preferably.
In addition, the multipolymers that form after the 2-hydroxyethyl methacrylate copolymerization etc. are also useful.This polymkeric substance can use after amount is mixed arbitrarily.
Except above-mentioned, can also enumerate (methyl) vinylformic acid 2-hydroxy propyl ester/Group-capped Polystyrene Macromer of putting down in writing in the Unexamined Patent 7-140654 communique/benzyl methacrylate/Sipacril 2739OF, vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester/polymethylmethacrylate macromonomer/benzyl methacrylate/Sipacril 2739OF, 2-hydroxyethyl methacrylate/Group-capped Polystyrene Macromer/methyl methacrylate/Sipacril 2739OF, 2-hydroxyethyl methacrylate/Group-capped Polystyrene Macromer/benzyl methacrylate/Sipacril 2739OF etc.
About the concrete structure unit of alkali soluble resins, particularly preferably (methyl) but vinylformic acid and the formed multipolymer of other monomer of copolymerization with it.
As above-mentioned can with other monomer of (methyl) acrylic acid copolymer, can list (methyl) alkyl acrylate, (methyl) vinylformic acid aryl ester, vinyl compound etc.Here, the hydrogen atom on alkyl and the aryl can be substituted the base replacement.
Object lesson as above-mentioned (methyl) alkyl acrylate and (methyl) vinylformic acid aryl ester can list (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) phenyl acrylate, benzyl acrylate, CA, vinylformic acid naphthalene ester, cyclohexyl acrylate etc.
In addition, as above-mentioned vinyl compound, for example can list vinylbenzene, alpha-methyl styrene, Vinyl toluene, glycidyl methacrylate, vinyl cyanide, vinyl-acetic ester, NVP, tetrahydrofurfuryl alcohol methacrylic ester, Group-capped Polystyrene Macromer, polymethylmethacrylate macromonomer, CH 2=CR 1R 2(R here, 1Expression hydrogen atom or carbonatoms are 1～5 alkyl, R 2The expression carbonatoms is 6～10 aromatic hydrocarbons ring.), CH 2=C (R 1) (COOR 3) (R here, 1Expression hydrogen atom or carbonatoms are 1～5 alkyl, R 3The expression carbonatoms is that 1～8 alkyl or carbonatoms are 6～12 aralkyl.) etc.
It is two or more that but other monomer of these copolymerization can be used alone or be used in combination.But other monomer of copolymerization is preferably from CH 2=CR 1R 2, CH 2=C (R 1) (COOR 3), select in (methyl) phenyl acrylate, (methyl) benzyl acrylate and the vinylbenzene at least a, particularly preferably be CH 2=CR 1R 2And/or CH 2=C (R 1) (COOR 3).The R here 1, R 2And R 3Implication with above-mentioned is identical respectively.
The content of alkali soluble resins is preferably 1～20 quality % with respect to the total solids composition of said composition in the Photocurable composition, and more preferably 2～15 quality % are particularly preferably 3～12 quality %.
(optical polymerism compound)
Photocurable composition of the present invention contains at least a optical polymerism compound.
The optical polymerism compound that can use among the present invention is the addition polymerization compound with at least one ethylenical unsaturated double bonds, be selected from have at least one, the preferred compound of terminal ethylenic unsaturated bond more than two.Such compound group is known in this industrial circle, can use these compounds among the present invention with being not particularly limited.They have such as monomer, prepolymer, are dipolymer, trimer and oligopolymer or their mixture and their chemical specieses such as multipolymer.Example as monomer and multipolymer thereof, can list: unsaturated carboxylic acid (for example, vinylformic acid, methacrylic acid, methylene-succinic acid, butenoic acid, methylacrylic acid, toxilic acid etc.) or its ester class, amides, preferably use the amides of ester, unsaturated carboxylic acid and the aliphatic polyamine compound formation of unsaturated carboxylic acid and aliphatic polyol compound formation.In addition, also can use aptly have hydroxyl, the addition reaction product of the esters of unsaturated carboxylic acids of the nucleophilic substitution base such as amino, sulfydryl or amides and simple function or polyfunctional isocyanate's class or epoxies and with dehydration condensation product of simple function or polyfunctional carboxylic acid etc.In addition, have the addition reaction product of the substituent esters of unsaturated carboxylic acids of electrophilicity such as isocyanate group or epoxy group(ing) or amides and simple function or polyfunctional alcohols, amine, thio-alcohol, and the substitution reaction product with the esters of unsaturated carboxylic acids of the substituents of leaving away such as halogen radical, tosyloxy or amides and simple function or polyfunctional alcohols, amine, thio-alcohol is fit to also.In addition, as other example, also can replace above-mentioned unsaturated carboxylic acid with the compound group that replaces to unsaturated phosphonic acids, vinylbenzene, vinyl ether etc.
The object lesson of the monomer of the ester that forms as aliphatic polyol compound and unsaturated carboxylic acid, as acrylate, have: ethylene glycol diacrylate, the diacrylate triethyleneglycol ester, diacrylate 1, the 3-butanediol ester, diacrylate 1, the 4-butanediol ester, the diacrylate propylene glycol ester, diacrylic acid pentyl diol ester, Viscoat 295, trimethylolpropane tris (acryloxy propyl group) ether, the trimethylolethane trimethacrylate acrylate, hexanediol diacrylate, diacrylate 1,4-cyclohexanediol ester, diacrylate TEG ester, the diacrylate pentaerythritol ester, pentaerythritol triacrylate, pentaerythritol tetracrylate, the diacrylate dipentaerythritol ester, six vinylformic acid dipentaerythritol ester, three vinylformic acid sorbitol esters, tetrapropylene acid sorbitol ester, five vinylformic acid sorbitol esters, six vinylformic acid sorbitol esters, isocyanuric acid three (acryloxy ethyl) ester, polyester acrylic ester oligomer etc., isocyanuric acid EO modification triacrylate etc.
As methacrylic ester, have: dimethacrylate 1, the 4-butanediol ester, the dimethacrylate triethyleneglycol ester, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, the trimethylolethane trimethacrylate methacrylic ester, Ethylene glycol dimethacrylate, dimethacrylate 1,3 butylene glycol ester, dimethacrylate hexylene glycol ester, the dimethacrylate pentaerythritol ester, trimethylammonium vinylformic acid pentaerythritol ester, pentaerythritol tetramethacrylate, the dimethacrylate dipentaerythritol ester, hexamethyl vinylformic acid dipentaerythritol ester, trimethylammonium vinylformic acid sorbitol ester, tetramethyl-vinylformic acid sorbitol ester, two [p-(3-methacryloxy-2-hydroxyl propoxy-) phenyl] dimethylmethane, two [p-(3-methacryloxy oxyethyl group) phenyl] dimethylmethane etc.
As itaconic ester, have: two methylene-succinic acid glycol esters, two methylene-succinic acid propylene glycol esters, two methylene-succinic acids 1,3-butanediol ester, two methylene-succinic acid BDO esters, two methylene-succinic acid tetramethylene glycol esters, two methylene-succinic acid pentaerythritol esters, four methylene-succinic acid sorbitol esters etc.As crotonate, have: dibutene acid glycol ester, dibutene acid BDO ester, dibutene acid pentaerythritol ester, four butenoic acid sorbitol esters etc.As methacrylic acid ester, have: di glycol ester, di pentaerythritol ester, four methylacrylic acid sorbitol esters etc.As maleic acid ester, have: two maleic acid glycol esters, two toxilic acid triethyleneglycol ester, two toxilic acid pentaerythritol esters, four toxilic acid sorbitol esters etc.
As the example of other ester, can use aptly such as the fatty alcohol of putting down in writing among examined patent publication 51-47334, the JP 57-196231 be put down in writing among the ester with aromatic series pastern bone frame put down in writing among ester class and JP 59-5240, JP 59-5241, the Unexamined Patent 2-226149, the Unexamined Patent 1-165613 contain amino ester etc.In addition, above-mentioned ester monomer also can be used as the mixture use.
In addition, the object lesson of the monomer of the acid amides that forms as aliphatic polyamine compound and unsaturated carboxylic acid, have: methylene-bisacrylamide, methylene-bis Methacrylamide, 1,6-hexa-methylene bisacrylamide, 1, the two Methacrylamides of 6-hexa-methylene, diethylenetriamine three acrylamides, xylylene bisacrylamide, the two Methacrylamides of xylylene etc.Example as other preferred acid amides is monomer can list: the acid amides with cyclohexylidene structure of putting down in writing among the examined patent publication 54-21726 is monomer.
In addition, using the urethane of the addition reaction preparation of isocyanic ester and hydroxyl is that the addition polymerization compound also is fit to, as such object lesson, can list: such as the polyisocyanate compounds that in a part, has two above isocyanate group of putting down in writing in the examined patent publication 48-41708 communique and the vinyl urethane compound that in a part, contains two above polymerizability vinyl that is formed by the vinyl monomer addition that contains hydroxyl of following general formula (A) expression etc.
CH 2＝C(R 34)COOCH 2CH(R 35)OH(A)
(wherein, in general formula (A), R 34And R 35Expression H or CH 3)
In addition, the urethane acrylate class of record in JP 51-37193 number, JP 2-32293 number, JP 2-16765 number, and the urethane compound class with oxyethane pastern bone frame of record in examined patent publication 58-49860 number, examined patent publication 56-17654 number, examined patent publication 62-39417 number, examined patent publication 62-39418 number also is fit to.In addition, in JP 63-277653 number, JP 63-260909 number, Unexamined Patent 1-105238 number, put down in writing, by using the addition polymerization compounds that in molecule, has amino structure or sulfide structure, can obtain the very excellent Photocurable composition of film speed.
As other example, can list: the polyester acrylate class of in JP 48-64183 number, examined patent publication 49-43191 number, examined patent publication 52-30490 number each communique, putting down in writing, make Resins, epoxy and the reaction of (methyl) vinylformic acid and polyfunctional acrylate and the methacrylic esters such as Epoxy Acrylates that obtain.In addition, can also list: the vinyl phosphonate based compound of record etc. in the specific unsaturated compound of record and Unexamined Patent 2-25493 number in examined patent publication 46-43946 number, JP 1-40337 number, JP 1-40336 number.In addition, in some cases, can use aptly the structure that contains perfluoroalkyl of record in JP 61-22048 number.Also can use in addition in the Japanese bonding will vol.20 of association, No.7,300～308 pages (1984) compound of being introduced as light solidified monomer and oligopolymer.
For these addition polymerization compounds, its structure, be used singly or in combination, the details of the using method such as addition can at random set according to the final functional design of Photocurable composition.For example, select from following viewpoint.
With regard to the viewpoint of sensitivity, the many structures of unsaturated group content that preferred per 1 molecule is average in the many situations of unsaturated group content, are preferably more than 2 official's energy.In addition, in order to improve the curing film strength, be preferably more than 3 official's energy.In addition, by being used in combination the compound of different functional number, different polymerizability base (for example acrylate, methacrylic ester, polystyrene compound, vinyl ether based compound), the method for regulating sensitivity and intensity also is effective.
In addition, for with Photocurable composition in other composition (for example, consistency, the dispersiveness of the binder polymers such as alkali soluble resins, Photoepolymerizationinitiater initiater, tinting material (pigment), the selection of addition polymerization compound, using method also are important key elements.The use of addition polymerization compound that for example, sometimes can be by low-purity or the addition polymerization compound combination more than two kinds make to improve the consistency with other compositions.
In addition, in order to improve the adhesivity with substrate etc., also can select specific structure.The addition polymerization Compound Phase for the non-volatility composition in the Photocurable composition preferably at 5～70 quality %, more preferably use in the scope of 10～60 quality.And can use separately, also can be used in combination.In addition, about the using method of addition polymerization compound, the viewpoints such as the size that can hinder according to the polymerization with respect to oxygen, exploring degree, fog density, variations in refractive index, surface adhesive are selected arbitrarily suitable structure, cooperation, addition.
(Photoepolymerizationinitiater initiater)
Photocurable composition of the present invention contains at least a Photoepolymerizationinitiater initiater.
As Photoepolymerizationinitiater initiater, can list the Lu that puts down in writing in the Unexamined Patent 57-6096 communique for example for the Jia oxadiazole; The halogenated methyl of record-s-triazine isoreactivity halogenide in JP 59-1281 communique, the JP 53-133428 communique etc.; The aromatic carbonyls such as ketal, acetal or benzoin alkylether class of putting down in writing in each specification sheets such as US Patent No. P-4318791, the open EP-88050A of European patent; The aromatic ketone compounds such as benzophenone of putting down in writing in the US Patent No. P-4199420 specification sheets; The xanthone of putting down in writing in the Fr-2456741 specification sheets (thioxanthone) class or acridine compound; The compounds such as the coumarins of putting down in writing in the Unexamined Patent 10-62986 communique or lophine (2,4,5-triphenyl imidazoles) dipolymer class; The sulfonium Organic Bor Complex of Unexamined Patent 8-015521 communique etc. etc.
Wherein, for Photocurable composition of the present invention; as Photoepolymerizationinitiater initiater; more preferably contain from the methyl phenyl ketone based compound; the ketal based compound; the benzophenone based compound; the bitter almond oil camphor based compound; the benzoyl based compound; the xanthone based compound; the triazine based compound; Lu is for Jia oxadiazole based compound; the acridine based compound; the coumarins based compound; lophine (2; 4; 5-triphenyl imidazoles) dipolymer class based compound; the bisglyoxaline based compound; the Photoepolymerizationinitiater initiater of selecting among the oxime compound etc.; particularly preferably contain from the triazine based compound; lophine (2; 4,5-triphenyl imidazoles) dipolymer class based compound; the Photoepolymerizationinitiater initiater of selecting among the oxime compound.
Photoepolymerizationinitiater initiater as above-mentioned methyl phenyl ketone system, for example can preferably list 2,2-diethoxy acetophenone, p-dimethylamino methyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, p-dimethylamino methyl phenyl ketone, 4 '-sec.-propyl-2-hydroxy-2-methyl-methyl phenyl ketone etc.
Photoepolymerizationinitiater initiater as above-mentioned ketal is can preferably list such as benzyl dimethyl ketal, benzyl-'beta '-methoxy ethyl acetals etc.
Photoepolymerizationinitiater initiater as above-mentioned benzophenone series, can preferably list for example benzophenone, 4,4 '-(two dimethylamino) benzophenone, 4,4 '-(two diethylin) benzophenone, 4,4 '-dichloro benzophenone, 1-hydroxyl-cyclohexyl-phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1,2-tolyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1,2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino acetone-1 etc.
Photoepolymerizationinitiater initiater as above-mentioned bitter almond oil camphor system or benzoyl base system can preferably list such as benzoin iso-propylether, bitter almond oil camphor ethyl isobutyl ether, benzoin methylether, methyl o-benzoyl yl benzoic acid ester etc.
Photoepolymerizationinitiater initiater as above-mentioned xanthone is can preferably list such as diethyl thioxanthone, di-isopropyl thioxanthone, single isopropyl thioxanthone, chloro thioxanthone etc.
Photoepolymerizationinitiater initiater as above-mentioned triazine system, for example can preferably list 2, two (the trichloromethyl)-6-p-p-methoxy-phenyls of 4--s-triazine, 2, two (the trichloromethyl)-6-p-methoxyl-styrenes of 4--s-triazine, 2, two (the trichloromethyl)-6-(1-p-dimethylamino phenyl)-1 of 4-, 3-butadienyl-s-triazine, 2, two (the trichloromethyl)-6-xenyls of 4--s-triazine, 2, two (the trichloromethyl)-6-(p-methyl biphenyl) of 4--s-triazine, p-hydroxyl-oxethyl styryl-2,6-two (trichloromethyl)-s-triazine, methoxyl-styrene-2,6-two (trichloromethyl)-s-triazine, 3,4-dimethoxy-styryl-2,6-two (trichloromethyl)-s-triazine, 4-benzo tetrahydrofuran-2,6-two (trichloromethyl)-s-triazine, 4-(o-bromo-p-N, N-(di ethoxy carbonyl is amino)-phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(p-N, N-(di ethoxy carbonyl is amino)-phenyl)-2,6-two (trichloromethyl)-s-triazine etc.
As the Photoepolymerizationinitiater initiater of above-mentioned Lu for Jia oxadiazole system, can preferably list for example 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(cyano-styrene base)-1,3,4-oxadiazole, 2-trichloromethyl-5-(naphthalene-1-yl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-styryl) styryl-1,3,4-oxadiazole etc.
Photoepolymerizationinitiater initiater as above-mentioned acridine is can preferably list for example 9-phenylacridine, 1, two (9-acridyl) heptane of 7-etc.
As the Photoepolymerizationinitiater initiater that above-mentioned coumarins is, can preferably list such as amino ((s-triazine-2-yl) the amino)-3-phenyl tonka bean camphor of 3-methyl-5-, 3-chloro-5-diethylin-((s-triazine-2-yl) amino)-3-phenyl tonka bean camphor, 3-butyl-5-dimethylamino-((s-triazine-2-yl) amino)-3-phenyl tonka bean camphor etc.
As above-mentioned lophine (2,4,5-triphenyl imidazoles) Photoepolymerizationinitiater initiater of dipolymer class system, can preferably list for example 2-(o-chlorophenyl)-4,5-diphenyl-imidazole base dipolymer, 2-(o-p-methoxy-phenyl)-4,5-diphenyl-imidazole base dipolymer, 2-(2,4-Dimethoxyphenyl)-4,5-diphenyl-imidazole base dipolymer etc.
Photoepolymerizationinitiater initiater as above-mentioned bisglyoxaline is can preferably list for example 2-mercaptobenzimidazole, 2,2 '-benzothiazole based bisulfide etc.
Photoepolymerizationinitiater initiater as above-mentioned oxime system; for example can list 1-phenyl-1; 2-propanedione-2-(o-ethoxy carbonyl) oxime; o-benzoyl-4 '-(benzo sulfydryl) benzoyl-hexyl-ketoxime, and in J.C.S Perkin II (1979) p1653～1660; J.C.S Perkin II (1979) p156～162; Journal of Photopolymer Science andTechnology (nineteen ninety-five) p202～232; JP 2000-66385 communique; JP 2000-80068 communique; the compound of record in the special table 2004-534797 communique etc.
Photoepolymerizationinitiater initiater as beyond above-mentioned can list 2,4,6-trimethylphenyl carbonyl-diphenylphosphine acyl-oxygen compound, hexafluoro phosphoro group trialkyl benzene base phosphonium salt etc.
Operable Photoepolymerizationinitiater initiater is not limited to above Photoepolymerizationinitiater initiater in the present invention, also can use other known Photoepolymerizationinitiater initiater.For example, can list the vicinal polyketoaldonyl compound of putting down in writing in No. 2367660 specification sheets of United States Patent (USP), the alpha-carbonyl compound of putting down in writing in No. the 2367661st, United States Patent (USP) and No. 2367670 specification sheets, the acyloin ether of putting down in writing in No. 2448828 specification sheets of United States Patent (USP), the aromatic series acyloin compound that is replaced by α-alkyl of putting down in writing in No. 2722512 specification sheets of United States Patent (USP), the multinuclear naphtoquinone compounds of putting down in writing in No. the 3046127th, United States Patent (USP) and No. 2951758 specification sheets, the combination of the triallyl imidazole dimer of putting down in writing in No. 3549367 specification sheets of United States Patent (USP)/p-aminophenyl ketone, benzothiazole based compound/trihalomethyl group of putting down in writing in the examined patent publication 51-48516 communique-s-triazine based compound etc.
In addition, these Photoepolymerizationinitiater initiaters also can be used in combination.
As the content of the Photoepolymerizationinitiater initiater in Photocurable composition, with respect to all solids composition of said composition, be preferably 0.1～15.0 quality %, more preferably 0.5～10.0 quality %.When the content of Photoepolymerizationinitiater initiater is in the above-mentioned scope time, can carry out well polyreaction and form the good film of intensity.
In Photocurable composition of the present invention, for the free-radical generating efficient that improves Photoepolymerizationinitiater initiater (radical initiator), the long wavelengthization of wavelength photoreceptor, also can contain sensitizing agent.
As being used for sensitizing agent of the present invention, preferably carry out the compound of sensitizing with electronic migration mechanism or energy migration mechanism for radical initiator.
As being used for sensitizing agent of the present invention, can list: the compound that belongs to the following compounds of enumerating and have absorbing wavelength in the wavelength region may of 300～450nm.
As the example of preferred sensitizing agent, can list: the compound that belongs to following compounds and have absorbing wavelength in 330～450nm zone.
For example, can list: the polynuclear aromatic same clan (for example, luxuriant and rich with fragrance, anthracene, pyrene perylene, benzo [9,10] phenanthrene, 9,10-dialkoxy anthracene), the xanthene class (for example, fluorescein, eosin, tetraiodofluorescein, rhodamine B, rose-red), thioxanthene ketone (isopropyl thioxanthone, diethyl thioxanthone, chloro thioxanthone), cyanine class (thiono cyanine for example, the oxo carbocyanine), the merocyanine class (for example, merocyanine, the carbonyl merocyanine), phthalocyanines, thiazides (for example, thionine, methylenum coeruleum, toluidine blue), acridine (for example, acridine orange, chloroflavin, trypaflavine), Anthraquinones (for example, anthraquinone), salt (for example in the squaric acid, the squaric acid inner salt), acridine orange, coumarins (for example, 7-diethylin-4-methylcoumarin), the oxo tonka bean camphor, phenothiazines, the azophenlyene class, styryl benzene class, azo-compound, ditan, triphenyl methane, distyryl benzene type, carbazoles, porphyrin, spirocyclic compound, the quinoline Azone, indigo, styryl, the pyranium salt compound, the methylene azole compounds, the pyrazoles triazole compounds, benzothiazole compound, the barbituric acid derivative, the Malony Ithiourea derivative, methyl phenyl ketone, benzophenone, thioxanthone, the aromatic ketone compounds such as Michler's keton, the heterogeneous ring compounds such as N-Fang oxazolidinone etc.
Photocurable composition of the present invention also preferably contains common sensitizing agent.In the Photocurable composition of the present invention altogether sensitizing agent have further raising sensitizing coloring matter and initiator to the sensitivity of active radioactive rays or the effects such as polymerization obstruction of the polymerizable compound that suppresses to produce because of oxygen.
As so common sensitizing agent; can list: amine; such as work " Journal of Polymer Society " 3173 pages of the 10th volumes (1972) such as M.R.Sander; examined patent publication 44-20189 communique; JP 51-82102 communique; JP 52-134692 communique; JP 59-138205 communique; JP 60-84305 communique; JP 62-18537 communique; JP 64-33104 communique; the compound of record etc. among No. 33825, the Research Disclosure; specifically, can list: trolamine; the p-dimethyl ethyl aminobenzoate; p-formyl radical xylidine; p-methylthio group xylidine etc.
Other example as common sensitizing agent, can list: mercaptan and sulfide-based, such as JP 53-702 communique, examined patent publication 55-500806 communique, the mercaptan compound of Unexamined Patent 5-142772 communique record, the di-sulphide compounds of JP 56-75643 communique etc., specifically, can list: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-4 (3H)-quinazoline, β-mercaptonaphthalene etc.
In addition, as other example, can list: amino-acid compound (for example, N-phenylglycines etc.), the organometallic compound of examined patent publication 48-42965 communique record (for example, tributyl tin acetate etc.), the sulphur compound of the hydrogen donor of examined patent publication 55-34414 communique record, the record of Unexamined Patent 6-308727 communique (for example, thioformaldehyde etc.) etc.
Improve the viewpoint of curing speed from the balance that is shifted by polymerization rate of growth and chain, the content of these common sensitizing agents is the scope of 0.1～30 quality % with respect to the quality optimization of the whole solids component of solidification compound, the more preferably scope of 1～25 quality %, the more preferably scope of 0.5～20 quality %.
Then, the composition beyond above-mentioned is described.
[solvent]
Photocurable composition of the present invention can suitably prepare with solvent with mentioned component usually.
As solvent, can list: the ester class, vinyl acetic monomer for example, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, the oxo ritalin, the oxo vinyl acetic monomer, the oxo N-BUTYL ACETATE, Methoxy Methyl Acetate, the Methoxy acetic acid ethyl ester, the Methoxy acetic acid butyl ester, the oxyethyl group ritalin, the oxyethyl group vinyl acetic monomer, and the 3-oxo alkyl propionates classes such as 3-oxo methyl propionate and 3-oxo ethyl propionate (for example, the 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate), and Acetylformic acid methyl esters, ethyl 2-oxopropanoate, with Acetylformic acid alkyl esters (for example, 2-methoxy methyl propionates such as Acetylformic acid propyl ester, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-oxo-2 Methylpropionic acid methyl esters, 2-oxo-2 Methylpropionic acid ethyl ester, 2-methoxyl group-2 Methylpropionic acid methyl esters, 2-oxyethyl group-2 Methylpropionic acid ethyl ester), and Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, Propyl pyruvate, methyl acetoacetate, ethyl 3-oxobutanoate, the 2-Oxobutyric acid methyl esters, 2-Oxobutyric acid ethyl ester etc.;
Ethers, such as diglyme, tetrahydrofuran (THF), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl glycol acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate (being also referred to as 2-acetoxyl group-1-methoxy propane in this specification sheets), dihydroxypropane single-ether acetic ester, propylene glycol monopropyl ether acetic ester etc.;
Ketone, such as methylethylketone, pimelinketone, 2-heptanone, 3-heptanone etc.;
Aromatic hydrocarbon based, such as toluene, dimethylbenzene etc.
In these solvents, preferably 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diglyme, N-BUTYL ACETATE, 3-methoxy methyl propionate, 2-heptanone, pimelinketone, ethyl carbitol acetic ester, diethylene glycol monobutyl ether acetic ester, propylene glycol monomethyl ether acetate etc.
Solvent can also be used in combination more than two kinds except can using separately.
[other composition]
In Photocurable composition of the present invention, can contain as required the various additives such as macromolecular compound beyond fluorine series organic compound, thermal polymerization inhibitor, weighting agent, specific pigment dispersion agent and the above-mentioned alkali soluble resins, tensio-active agent, adhesion promoter, antioxidant, UV light absorber, aggregation inhibitor.
＜fluorine series organic compound 〉
By containing the fluorine series organic compound, when making coating fluid, can improve characteristics of liquids (particularly mobile), can improve the homogeneity of coating thickness or economize fluidity.Namely, owing to can improve wetting property to substrate by the surface tension that reduces substrate and coating fluid, raising is to the coating of substrate, even so when forming the film of approximate number μ m with a small amount of liquid measure, also can form the film of the little uniform thickness of thickness deviation, be effective with regard to this point.
The fluorine content of fluorine series organic compound is preferably 3～40 quality %, and more preferably 5～30 quality % are particularly preferably 7～25 quality %.When fluorine content is in above-mentioned scope, be resultful with regard to the coating thickness homogeneity with the viewpoint of economizing fluidity, the solvability in composition is also good.
As the fluorine series organic compound, can list for example MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F177, MEGAFACEF141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144, MEGAFACE R30, MEGAFACE F437 (above is Dainippon Ink. ﹠ Chemicals Inc's system); Fluorad FC430, Fluorad FC431, Fluorad FC171 (above is Sumitomo 3M Co., Ltd. system); Surflon S-382, Surflon SC-101, Surflon SC-103, SurflonSC-104, Surflon SC-105, Surflon SC-1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above is Asahi Glass Co., Ltd's system) etc.
The fluorine series organic compound is particularly for for example preventing when making the coated film attenuation of coating formation that it is effective being coated with not even thickness irregular.In addition, also be effective even be coated with in the method at the seam that is easy to produce disconnected liquid.
The add-on of fluorine series organic compound is preferably 0.001～2.0 quality % with respect to the total mass of pigment dispensing composition or Photocurable composition, more preferably 0.005～1.0 quality %.
＜thermal polymerization 〉
It also is effective containing thermal polymerization in Photocurable composition of the present invention.As thermal polymerization; can list for example various azo based compounds, superoxide based compound; as above-mentioned azo based compound; can list azo two based compounds; as above-mentioned superoxide based compound, can list ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl, peroxidation diacyl, peroxyester, peroxy dicarbonate etc.
＜tensio-active agent 〉
In Photocurable composition of the present invention, from improving the viewpoint of coating, preferably consist of with various tensio-active agents, can use the various tensio-active agents of nonionic system, positively charged ion system, negatively charged ion system.Wherein, be in the tensio-active agent at nonionic, the fluorine that preferably has perfluoroalkyl is tensio-active agent.
Be the object lesson of tensio-active agent as fluorine, can list MEGAFACE (registered trademark) series of Dainippon Ink. ﹠ Chemicals Inc's system, Fluorad (registered trademark) series of 3M company system etc.
Except above-mentioned, in Photocurable composition, as the object lesson of additive, can list the weighting agents such as glass, aluminum oxide; Itaconic acid copolymer, butenoic acid multipolymer, maleic acid, partial esterification maleic acid, acid cellulose derivative, the polymkeric substance with hydroxyl and acid anhydrides addition and the material that forms, pure soluble nylon, the soluble resin of the alkali such as phenoxy resin that is formed by dihydroxyphenyl propane and Epicholorohydrin; The tensio-active agents such as nonionic system, positively charged ion system, negatively charged ion system are in particular phthalocyanine derivates (commercially available product EFKA-745 (gloomy lower industry company system)); The positively charged ions such as organosiloxane polymer KP341 (chemical industrial company of SHIN-ETSU HANTOTAI system), (methyl) acrylic acid series (being total to) polymkeric substance polyflow No.75, No.90, No.95 (oil chemical industry company of common prosperity society system), WO01 (abundant merchant company system) are tensio-active agent;
Example as other additive etc., can list polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylplenyl ether, two lauric acid macrogol esters, distearyl acid polyethylene glycol ester, sorbitan fatty acid esters (BASF AG's system, Pluronic L10, L31, L61, L62,10R5,17R2,25R2, the nonionics such as Tetronic 304,701,704,901,904,150R1 are tensio-active agent; The negatively charged ion such as W004, W005, W017 (abundant merchant company system) are tensio-active agent; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (more than be gloomy lower industry company system), Disperse Aid 6, Disperse Aid 8, the macromolecule dispersing agents such as Disperse Aid 15, Disperse Aid 9100 (SANNOPCO company system); Solspers 3000,5000,9000,12000,13240,13940,17000,24000,26000, the various Solspers dispersion agents (ZENECA Co., Ltd. system) such as 28000; ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (rising sun electrification Co., Ltd. system) and ISONET S-20 (Sanyo Chemical Industries Co., Ltd.'s system); The UV light absorber such as 2-(the 3-tertiary butyl-5-methyl-2-hydroxy phenyl)-5-chlorinated benzotriazole, alkoxy benzophenone; And the aggregation inhibitor such as sodium polyacrylate.
In addition, when the alkali dissolution that promotes uncured portion when expecting the development of further raising Photocurable composition, can in Photocurable composition, add organic carboxyl acid, preferred molecular weight is the lower molecular weight organic carboxyl acid below 1000.Particularly, can list such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, diethylacetic acid, enanthic acid, the aliphatics monocarboxylic acid such as sad; The aliphatic dicarboxylic acids such as oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, brazilic acid, Methylpropanedioic acid, ethyl malonic acid, dimethyl malonic acid, pyrovinic acid, tetramethyl-succinic acid, citraconic acid; The aliphatics tribasic carboxylic acids such as tricarballylic acid, equisetic acid, camphoronic acid; Phenylformic acid, toluic acid, cuminic acid, 2，3-xylic acid, 3, the aromatic series monocarboxylic acids such as 5-mesitylenic acid; The aromatic polycarboxylic acids such as phthalic acid, m-phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, inclined to one side benzene tetracarboxylic acid, pyromellitic acid; Other carboxylic acids such as phenylacetic acid, hydratropic acid, phenylpropionic acid, amygdalic acid, phenylsuccinic acid, atropic acid, styracin, methyl cinnamate, cinnamein, cinnamylidene acetic acid, coumaric acid, umbellic acid.
＜thermal polymerization inhibitor 〉
In the Photocurable composition of the present invention, also preferred the adding thermal polymerization inhibitor is arranged, for example, usefully quinhydrones, p-methoxyphenol, di-t-butyl-p-cresols, pyrogallol, tert-butyl catechol, benzoquinones, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole etc.
Photocurable composition of the present invention can contain alkali soluble resins, optical polymerism compound and Photoepolymerizationinitiater initiater (preferably with solvent), and prepare to additives such as mixed surfactants wherein as required by making above-mentioned pigment dispensing composition of the present invention.
＜colour filter and manufacture method thereof 〉
Colour filter of the present invention is made by using above-mentioned pigment dispensing composition of the present invention to form painted film (colored pattern) at substrates such as glass.
Specifically, with Photocurable composition of the present invention directly or across other layer apply (preferably with spin coating, seam be coated with, the coating processes such as curtain coating coating, roller coat are coated with) to substrate, form photosensitive film.On the photosensitive film that forms, Jie is exposed by the mask pattern of regulation, remove uncured portion with developing liquid developing after the exposure, thereby form the colored pattern (for example colored pixels) of shades of colour (for example three looks or four looks), can the most compatibly make colour filter thus.
Thus, the difficulty of employed colour filter aspect complete processing diminishes in liquid crystal display device or the solid-state imager, can high quality and make at low cost.
At this moment, as the radioactive rays that exposure is used, the particularly preferably ultraviolet rays such as g line, h line, i line, j line.
Can use hot-plate, baking oven etc. in 50～140 ℃ temperature range, under 10～300 seconds condition, to carry out by the drying (prebake conditions) that applies the film that (being preferably coating) make to the Photocurable composition of the present invention on the substrate.
When developing, the uncured portion after the exposure is washed out, only residual cured portion in developing solution.Development temperature is generally 20～30 ℃, and development time is 20～90 seconds.
As developing solution, can use any developing solution, do not make the solution of cured portion dissolving so long as make the film dissolving of the Photocurable composition in the uncured portion just.Specifically, can use the combination of various organic solvents or the aqueous solution of alkalescence.
As above-mentioned organic solvent, can list the above-mentioned solvent that when preparation pigment dispensing composition of the present invention or Photocurable composition, can use.
The aqueous solution as above-mentioned alkalescence, can list and for example make sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, water glass, Starso, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrroles, piperidines, 1,8-diazabicylo-[5,4,0]-basic cpds such as 7-undecylene according to concentration be 0.001～10 quality %, the mode that is preferably 0.01～1 quality % dissolves the alkaline aqueous solution that forms.
In addition, when alkaline aqueous solution was used as developing solution, water washed (rinse) after development usually.
After the development, unnecessary developing solution is removed in washing, carry out drying after, usually under 100～240 ℃ temperature, carry out heat treated (rear baking).Above-mentioned rear baking is be used to the heating after the development that makes completion of cure, usually carries out about 200～250 ℃ of heating (hard baking).Should rear baking processing can use hot-plate and the heater meanses such as convection oven (warm braw circulating drying machine), high frequency heating machine according to above-mentioned condition by the coated film after will developing, carry out with continous way or intermittent type.
By making aforesaid operations consistent with desirable tone number, every kind of color is repeated successively, can make the colour filter of the painted cured film that has formed multiple color.
When Photocurable composition of the present invention being applied to when forming film on the substrate, as the dry thickness of film, be generally 0.3～5.0 μ m, be preferably 0.5～3.5 μ m, most preferably be 1.0～2.5 μ m.
As substrate, can list such as the non-alkali glass, soda glass, Pai Ruikesi (registered trademark) glass, the silica glass that are used for liquid crystal display device etc. and on them, adhere to nesa coating and the substrate that forms and be used for the photo-electric conversion element substrate of solid-state imager etc., such as silicon substrate etc. and plastic base.On these substrates, usually form the secret note (black stripe) with each pixel isolation.
As plastic base, preferably have in its surface gas-barrier layer and/or solvent resistance layer.
When Photocurable composition when being applied on the substrate, as other layer, can be listed gas-barrier layer, solvent resistance layer etc. across other layer.
In the above-mentioned explanation, as the purposes of pigment dispensing composition of the present invention and Photocurable composition, mainly be centered by the purposes of colour filter, to describe, but also be applicable to form the black matrix" of each colored pixels isolation that will consist of colour filter.
Above-mentioned black matrix" can form by following method: use and adopted the black pigments such as carbon black, titanium be black to carry out pattern exposure, development as the Photocurable composition of the present invention (pigment dispensing composition) of pigment, then carry out as required the curing that rear baking promotes film again.
[embodiment]
Below, more specifically describe the present invention by embodiment, but the present invention is only otherwise exceed its purport just, is not subjected to the restriction of following embodiment.In addition, unless otherwise specified, " part " expression " mass parts ".
[synthesis example 1]
(synthesizing of monomer 1)
9.51 parts of 2-aminopyrimidines are dissolved in 30 parts of pyridines, are heated to 45 ℃.To wherein dripping 17.1 parts of isocyanic acid 2-methacryloxy ethyl esters, further heated and stirred are 5 hours under 50 ℃.This reaction solution is poured in 200 parts of distilled water while stirring, with resulting precipitate filtering separation, cleaned, obtain thus 23.8 parts of monomers 1 (above-mentioned exemplary compounds M-2).
(synthesizing of polymkeric substance 1)
East Asia Synesis Company system), 7.5 parts of methacrylic acids and 116.7 parts of 1-methoxy-2-propanols pack in the there-necked flask behind nitrogen replacement the polymethylmethacrylate (AA-6: that 5.0 parts of above-mentioned monomers, 37.5 parts is had endways methacryloyl; with stirrer (new eastern science Co., Ltd.: ス リ one ワ Application モ one タ (three one motor)) stir; the limit passes into the heating of nitrogen limit in flask, be warming up to 78 ℃.To wherein adding 0.1 part 2, two (2 Methylpropionic acid) dimethyl esters (with the pure medicine of light Co., Ltd.'s system " V-601 ") of 2 '-azo were in 78 ℃ of heated and stirred 2 hours.After 2 hours, add 0.1 part of V-601, heated and stirred 3 hours obtains 30% solution of polymkeric substance 1 (above-mentioned exemplary compounds (2)) again.
[synthesis example 2]
(synthesizing of monomer 2)
13.3 parts of 2-aminobenzimidazoles are dissolved in 30 parts of pyridines, are heated to 45 ℃.To wherein dripping 17.1 parts of isocyanic acid 2-methacryloxy ethyl esters, further heated and stirred are 5 hours under 50 ℃.This reaction solution is poured in 200 parts of distilled water while stirring, with resulting precipitate filtering separation, cleaned, obtain thus 27.3 parts of monomers 2 (above-mentioned exemplary compounds M-4).
(synthesizing of polymkeric substance 2)
East Asia Synesis Company system), 7.5 parts of methacrylic acids and 116.7 parts of 1-methoxy-2-propanols pack in the there-necked flask behind nitrogen replacement the polymethylmethacrylate (AA-6: that 5.0 parts of above-mentioned monomers 2,37.5 parts is had endways methacryloyl; with stirrer (new eastern science Co., Ltd.: ス リ one ワ Application モ one タ) stir; the limit passes into the heating of nitrogen limit in flask, be warming up to 78 ℃.To wherein adding 0.1 part 2, two (2 Methylpropionic acid) dimethyl esters (with the pure medicine of light Co., Ltd.'s system " V-601 ") of 2 '-azo were in 78 ℃ of heated and stirred 2 hours.After 2 hours, add 0.1 part of V-601, heated and stirred 3 hours obtains 30% solution of polymkeric substance 2 (above-mentioned exemplary compounds (6)) again.
[synthesis example 3]
(synthesizing of polymkeric substance 3)
East Asia Synesis Company system), 7.5 parts of methacrylic acids, 0.90 part of n-dodecane mercaptan and 116.7 parts of 1-methoxy-2-propanols pack in the there-necked flask behind nitrogen replacement the polymethylmethacrylate (AA-6: that 5.0 parts of above-mentioned monomers 2,37.5 parts is had endways methacryloyl; with stirrer (new eastern science Co., Ltd.: ス リ one ワ Application モ one タ) stir; the limit passes into the heating of nitrogen limit in flask, be warming up to 75 ℃.To wherein adding 0.26 part 2, two (2 Methylpropionic acid) dimethyl esters (with the pure medicine of light Co., Ltd.'s system " V-601 ") of 2 '-azo were in 75 ℃ of heated and stirred 3 hours.Add 0.26 part of V-601, heated and stirred adds 0.26 part of V-601 after 3 hours again, carries out 3 hours heated and stirred again, obtains thus 30% solution of polymkeric substance 3 (above-mentioned exemplary compounds (17)).
[synthesis example 4]
(synthesizing of polymkeric substance 4)
East Asia Synesis Company system), 5.0 parts of vinylformic acid, 0.76 part of n-dodecane mercaptan and 116.7 parts of 1-methoxy-2-propanols pack in the there-necked flask behind nitrogen replacement the polystyrene (AS-6: that 5.0 parts of above-mentioned monomers 2,40.0 parts is had endways methacryloyl; with stirrer (new eastern science Co., Ltd.: ス リ one ワ Application モ one タ) stir; the limit passes into the heating of nitrogen limit in flask, be warming up to 75 ℃.To wherein adding 0.22 part 2, two (2 Methylpropionic acid) dimethyl esters (with the pure medicine of light Co., Ltd.'s system " V-601 ") of 2 '-azo were in 75 ℃ of heated and stirred 3 hours.Add 0.22 part of V-601, heated and stirred adds 0.22 part of V-601 after 3 hours again, carries out 3 hours heated and stirred again, obtains thus 30% solution of polymkeric substance 4 (above-mentioned exemplary compounds (18)).
[synthesis example 5]
(synthesizing of polymkeric substance 5)
With 4.0 parts of above-mentioned monomers 2; 38.5 part has the polymethylmethacrylate (AA-6: East Asia Synesis Company system) of methacryloyl endways; 7.5 succinyl oxide affixture (the Xin Zhong village KCC system of part 2-hydroxyethyl methacrylate; NK ESTER SA: structure is as follows); 0.43 part n-dodecane mercaptan and 116.7 parts of 1-methoxy-2-propanols are packed in the there-necked flask behind nitrogen replacement; with stirrer (new eastern science Co., Ltd.: ス リ one ワ Application モ one タ) stir; the limit passes into the heating of nitrogen limit in flask, be warming up to 75 ℃.To wherein adding 0.12 part 2, two (2 Methylpropionic acid) dimethyl esters (with the pure medicine of light Co., Ltd.'s system " V-601 ") of 2 '-azo were in 75 ℃ of heated and stirred 3 hours.Add 0.12 part of V-601, heated and stirred adds 0.12 part of V-601 after 3 hours again, carries out 3 hours heated and stirred again, obtains thus 30% solution of polymkeric substance 5 (above-mentioned exemplary compounds (19)).
Figure S2007101483983D00391
[synthesis example 6]
(synthesizing of polymkeric substance 6)
East Asia Synesis Company system), 5.0 parts of vinylformic acid, 5.0 parts of benzyl methacrylates, 0.98 part of n-dodecane mercaptan and 116.7 parts of 1-methoxy-2-propanols pack in the there-necked flask behind nitrogen replacement the polymethylmethacrylate (AA-6: that 5.0 parts of above-mentioned monomers 2,35.0 parts is had endways methacryloyl; with stirrer (new eastern science Co., Ltd.: ス リ one ワ Application モ one タ) stir; the limit passes into the heating of nitrogen limit in flask, be warming up to 75 ℃.To wherein adding 0.28 part 2, two (2 Methylpropionic acid) dimethyl esters (with the pure medicine of light Co., Ltd.'s system " V-601 ") of 2 '-azo were in 75 ℃ of heated and stirred 3 hours.Add 0.28 part of V-601, heated and stirred adds 0.28 part of V-601 after 3 hours again, carries out 3 hours heated and stirred again, obtains thus 30% solution of polymkeric substance 6 (above-mentioned exemplary compounds (20)).
[synthesis example 7]
(synthesizing of monomer 3)
15.0 parts of 2-mercaptobenzimidazoles, 13.8 parts of salt of wormwood are dissolved in 30 parts of dimethyl sulfoxide (DMSO), are heated to 45 ℃.To wherein dripping 22.9 parts of 1-chloro-4-methyl-benzenes, further heated and stirred are 5 hours under 50 ℃.This reaction solution is poured in 200 parts of distilled water while stirring, with resulting precipitate filtering separation, cleaned, obtain thus 25.6 parts of monomers 3 (above-mentioned exemplary compounds M-10).
(synthesizing of polymkeric substance 7)
East Asia Synesis Company system), 7.5 parts of methacrylic acids and 116.7 parts of 1-methoxy-2-propanols pack in the there-necked flask behind nitrogen replacement the polymethylmethacrylate (AA-6: that 5.0 parts of above-mentioned monomers 3,37.5 parts is had endways methacryloyl; with stirrer (new eastern science Co., Ltd.: ス リ one ワ Application モ one タ) stir; the limit passes into the heating of nitrogen limit in flask, be warming up to 78 ℃.To wherein adding 0.1 part 2, two (2 Methylpropionic acid) dimethyl esters (with the pure medicine of light Co., Ltd.'s system " V-601 ") of 2 '-azo were in 78 ℃ of heated and stirred 2 hours.After 2 hours, add 0.1 part of V-601, heated and stirred 3 hours obtains 30% solution of polymkeric substance 7 (above-mentioned exemplary compounds (14)) again.
[synthesis example 8]
(synthesizing of polymkeric substance 8)
East Asia Synesis Company system), 5.0 parts of vinylformic acid, 0.84 part of n-dodecane mercaptan and 116.7 parts of 1-methoxy-2-propanols pack in the there-necked flask behind nitrogen replacement the polymethylmethacrylate (AA-6: that 7.5 parts of above-mentioned monomers 3,37.5 parts is had endways methacryloyl; with stirrer (new eastern science Co., Ltd.: ス リ one ワ Application モ one タ) stir; the limit passes into the heating of nitrogen limit in flask, be warming up to 75 ℃.To wherein adding 0.24 part 2, two (2 Methylpropionic acid) dimethyl esters (with the pure medicine of light Co., Ltd.'s system " V-601 ") of 2 '-azo were in 75 ℃ of heated and stirred 3 hours.Add 0.24 part of V-601, heated and stirred adds 0.24 part of V-601 after 3 hours again, carries out 3 hours heated and stirred again, obtains thus 30% solution of polymkeric substance 8 (above-mentioned exemplary compounds (21)).
[synthesis example 9]
(synthesizing of monomer 4)
16.7 parts of 2-mercaptobenzothiazoles, 13.8 parts of salt of wormwood are dissolved in 30 parts of dimethyl sulfoxide (DMSO), are heated to 45 ℃.To wherein dripping 22.9 parts of 1-chloro-4-methyl-benzenes, further heated and stirred are 5 hours under 50 ℃.This reaction solution is poured in 200 parts of distilled water while stirring, with resulting precipitate filtering separation, cleaned, obtain thus 26.9 parts of monomers 4 (above-mentioned exemplary compounds M-11).
(synthesizing of polymkeric substance 9)
East Asia Synesis Company system), 5.0 parts of methacrylic acids, 0.74 part of n-dodecane mercaptan and 116.7 parts of 1-methoxy-2-propanols pack in the there-necked flask behind nitrogen replacement the polymethylmethacrylate (AA-6: that 7.5 parts of above-mentioned monomers 4,37.5 parts is had endways methacryloyl; with stirrer (new eastern science Co., Ltd.: ス リ one ワ Application モ one タ) stir; the limit passes into the heating of nitrogen limit in flask, be warming up to 75 ℃.To wherein adding 0.21 part 2, two (2 Methylpropionic acid) dimethyl esters (with the pure medicine of light Co., Ltd.'s system " V-601 ") of 2 '-azo were in 75 ℃ of heated and stirred 3 hours.Add 0.21 part of V-601, heated and stirred adds 0.21 part of V-601 after 3 hours again, carries out 3 hours heated and stirred again, obtains thus 30% solution of polymkeric substance 9 (above-mentioned exemplary compounds (22)).
[synthesis example 10]
(synthesizing of polymkeric substance 10)
East Asia Synesis Company system), 5.0 parts of benzyl methacrylates, 0.50 part of n-dodecane mercaptan and 116.7 parts of 1-methoxy-2-propanols pack in the there-necked flask behind nitrogen replacement the polymethylmethacrylate (AA-6: that 7.5 parts of above-mentioned monomers 4,37.5 parts is had endways methacryloyl; with stirrer (new eastern science Co., Ltd.: ス リ one ワ Application モ one タ) stir; the limit passes into the heating of nitrogen limit in flask, be warming up to 75 ℃.To wherein adding 0.14 part 2, two (2 Methylpropionic acid) dimethyl esters (with the pure medicine of light Co., Ltd.'s system " V-601 ") of 2 '-azo were in 75 ℃ of heated and stirred 3 hours.Add 0.14 part of V-601, heated and stirred adds 0.14 part of V-601 after 3 hours again, carries out 3 hours heated and stirred again, obtains thus 30% solution of polymkeric substance 10 (above-mentioned exemplary compounds (23)).
[embodiment 1]
The modulation of＜pigment dispensing composition (R1) 〉
The composition of following composition (1) is mixed, mix 3 hours with clarifixator with revolution 3000r.p.m., modulation contains the mixing solutions of pigment.
(forming (1))
C.I. Pigment red is 254 90 parts
C.I. Pigment red is 177 10 parts
150 parts of 30% solution of polymkeric substance 1 (specific pigment dispersion agent)
750 parts of 2-acetoxyl groups-1-methoxy propane
Then, will be by the above-mentioned mixing solutions that makes further with bead dispersion machine DISPERMAT (the GETZMANN company system) dispersion treatment 6 hours of having used 0.3mm φ zirconium white bead, then further use high pressure dispersion machine NANO-3000-10 with reliever (Japanese BEE Co., Ltd. system) at 2000kg/cm 2Pressure under carry out dispersion treatment with flow 500g/min.This dispersion treatment repeats 10 times, obtains red pigment dispensing composition (R1).
The evaluation of＜pigment dispensing composition 〉
(R1) carries out following evaluation to resulting pigment dispensing composition.
(1) mensuration of viscosity, evaluation
For resulting pigment dispensing composition (R1), with E type viscometer, measure the viscosities il of the pigment dispensing composition (R1) after just having disperseed 1And the viscosities il of measuring the pigment dispensing composition after disperseing rear (under the room temperature) through a week 2, the degree of evaluation tackify.Evaluation result as described in Table 1.At this, viscosity is low to show that then the viscosity rise that is caused by dispersion agent is suppressed, and dispersiveness and the dispersion stabilization of pigment are good.
(2) mensuration of contrast gradient, evaluation
Resulting pigment dispensing composition (R1) is coated on the glass substrate, and the thickness of making dry rear coated film is the sample of 1 μ m.This sample is placed between 2 polaroids, measure polarization axle when parallel and the transmission light quantity when vertical, its ratio is spent as a comparison (this evaluation method with reference to " nineteen ninety the 7th color reversion glory learn コ Application Off ア レ Application ス, 512 color tables show 10.4 " サ イ ズ TFT-LCD with カ ラ one Off イ Le タ one (nineteen ninety the 7th color light association discuss, 512 looks demonstration 10.4 " size TFT-LCD colour filter), plant wood, Xiao Guan, good fortune forever, in the mountain ").The result of evaluation of measuring as described in Table 1.At this, the contrast gradient height then represents pigment with the state Uniform Dispersion of height miniaturization, so transmissivity is that tinting strength is high.
[embodiment 2～10]
Be that polymkeric substance 2～polymkeric substance 10 replaces with the specific pigment dispersion agent that makes in the above-mentioned synthesis example 2～10 respectively with the specific pigment dispersion agent among the embodiment 1 (polymkeric substance 1), in addition all modulate in the same manner red pigment dispensing composition (R2)～(R10) with embodiment 1, carry out the evaluation identical with embodiment 1.The result as described in Table 1.
[embodiment 11]
The pigment dispensing composition that red pigment dispersive composition among the embodiment 1 is obtained with the mixing solutions that contains veridian that uses following composition (2) replaces, in addition all modulate in the same manner green pigment dispensing composition (G1) with embodiment 1, carry out the evaluation identical with embodiment 1.The result as described in Table 2.
(forming (2))
C.I. pigment green 36 is 60 parts
C.I. Pigment Yellow 73 is 150 40 parts
150 parts of 30% solution of polymkeric substance 1 (specific pigment dispersion agent)
750 parts of 2-acetoxyl groups-1-methoxy propane
[embodiment 12～20]
The specific pigment dispersion agent (polymkeric substance 1) that uses among the embodiment 11 is replaced with above-mentioned polymkeric substance 2～polymkeric substance 10 (specific pigment dispersion agent), in addition all modulate in the same manner the dispersive composition (G2)～(G10) of veridian with embodiment 11, carry out the evaluation identical with embodiment 11.The result as described in Table 2.
[embodiment 21]
The pigment dispensing composition of the blueness that the pigment dispensing composition of the redness among the embodiment 1 is obtained with the mixing solutions that contains blue pigments that uses following composition (3) replaces, in addition all modulate in the same manner blue pigment dispensing composition (B1) with embodiment 1, carry out the evaluation identical with embodiment 1.The result as described in Table 3.
(forming (3))
C.I. pigment Blue 15; 6 85 parts
C.I. pigment Violet 23 is 15 parts
150 parts of 30% solution of polymkeric substance 1 (specific pigment dispersion agent)
750 parts of 2-acetoxyl groups-1-methoxy propane
[embodiment 22～30]
Use respectively above-mentioned polymkeric substance 2～polymkeric substance 10 (specific pigment dispersion agent) to replace in the polymkeric substance 1 among the embodiment 21 (specific pigment dispersion agent), in addition all modulate in the same manner blue pigment dispensing composition (B1)～(B10) with embodiment 21, carry out the evaluation identical with embodiment 21.The result as described in Table 3.
[comparative example 1]
Polymkeric substance 1 among the embodiment 1 (specific pigment dispersion agent) is replaced with EFKA4047 (EFKA company system) (hereinafter referred to as D-1), in addition all modulate in the same manner red pigment dispensing composition (R11) with embodiment 1, carry out the evaluation identical with embodiment 1.The result as described in Table 1.
[comparative example 2]
With the polymkeric substance 1 among the embodiment 1 (specific pigment dispersion agent) with N-vinyl imidazole and the terminal polymethyl methacrylate copolymer D-2 that has carried out the methacrylic acidylate (=15/85[mass ratio], weight-average molecular weight: 30000) replace; in addition all modulate in the same manner red pigment dispensing composition (R12) with embodiment 1, carry out the evaluation identical with embodiment 1.The result as described in Table 1.
[comparative example 3]
With the polymkeric substance 1 among the embodiment 1 (specific pigment dispersion agent) with methacrylic acid and the terminal polymethyl methacrylate copolymer D-3 that has carried out the methacrylic acidylate (=15/85[mass ratio], weight-average molecular weight: 30000) replace; in addition all modulate in the same manner red pigment dispensing composition (R13) with embodiment 1, carry out the evaluation identical with embodiment 1.The result as described in Table 1.
[comparative example 4]
With the polymkeric substance 1 among the embodiment 1 (specific pigment dispersion agent) with methacrylic acid 2-dimethylamino ethyl ester and the terminal polymethyl methacrylate copolymer D-4 that has carried out the methacrylic acidylate (=15/85[mass ratio], weight-average molecular weight: 20000) replace; in addition all modulate in the same manner red pigment dispensing composition (R14) with embodiment 1, carry out the evaluation identical with embodiment 1.The result as described in Table 1.
[comparative example 5]
With the polymkeric substance 1 among the embodiment 1 (specific pigment dispersion agent) with the monomer of following structure and the terminal polymethyl methacrylate copolymer D-5 that has carried out the methacrylic acidylate (=18/82[mass ratio], weight-average molecular weight: 20000) replace; in addition all modulate in the same manner red pigment dispensing composition (R15) with embodiment 1, carry out the evaluation identical with embodiment 1.The result as described in Table 1.
Figure S2007101483983D00451
[comparative example 6]
With the polymkeric substance 1 among the embodiment 1 (specific pigment dispersion agent) with the monomer of following structure and the terminal polymethyl methacrylate copolymer D-6 that has carried out the methacrylic acidylate (=18/82[mass ratio], weight-average molecular weight: 20000) replace; in addition all modulate in the same manner red pigment dispensing composition (R16) with embodiment 1, carry out the evaluation identical with embodiment 1.The result as described in Table 1.
Figure S2007101483983D00452
[comparative example 7～12]
Polymkeric substance 1 among the embodiment 11 (specific pigment dispersion agent) is used respectively any replacement of above-mentioned multipolymer D-1～D-6, in addition all modulate in the same manner green pigment dispensing composition (G11)～(G16) with embodiment 11, carry out the evaluation identical with embodiment 11.The result as described in Table 2.
[comparative example 13～18]
Above-mentioned polymkeric substance 1 (pigment dispersing agent) among the embodiment 21 is used respectively any replacement of above-mentioned multipolymer D-1～D-6, in addition all modulate in the same manner blue pigment dispensing composition (B11)～(B16) with embodiment 21, carry out the evaluation identical with embodiment 21.The result as described in Table 3.
[table 1]
The red pigment dispersive composition Pigment dispersing agent Viscosity after just having disperseed (mPas) Viscosity after 1 week (mPas) Contrast gradient
Embodiment 1 R1 Polymkeric substance 1 12 13 1250
Embodiment 2 R2 Polymkeric substance 2 8 9 1350
Embodiment 3 R3 Polymkeric substance 3 7 8 1350
Embodiment 4 R4 Polymkeric substance 4 8 9 1350
Embodiment 5 R5 Polymkeric substance 5 9 10 1350
Embodiment 6 R6 Polymkeric substance 6 8 9 1350
Embodiment 7 R7 Polymkeric substance 7 10 10 1300
Embodiment 8 R8 Polymkeric substance 8 9 10 1350
Embodiment 9 R9 Polymkeric substance 9 8 9 1350
Embodiment 10 R10 Polymkeric substance 10 8 8 1350
Comparative example 1 R11 D-1 25 250 1100
Comparative example 2 R12 D-2 20 400 950
Comparative example 3 R13 D-3 More than 1200 Gelation 900
Comparative example 4 R14 D-4 15 75 1150
Comparative example 5 R15 D-5 20 80 1150
Comparative example 6 R16 D-6 15 70 1150
[table 2]
The veridian dispersive composition Pigment dispersing agent Viscosity after just having disperseed (mPas) Viscosity after 1 week (mPas) Contrast gradient
Embodiment 11 G1 Polymkeric substance 1 14 14 1450
Embodiment 12 G2 Polymkeric substance 2 10 11 1500
Embodiment 13 G3 Polymkeric substance 3 9 9 1550
Embodiment 14 G4 Polymkeric substance 4 10 10 1550
Embodiment 15 G5 Polymkeric substance 5 11 11 1500
Embodiment 16 G6 Polymkeric substance 6 10 11 1500
Embodiment 17 G7 Polymkeric substance 7 15 16 1500
Embodiment 18 G8 Polymkeric substance 8 12 13 1500
Embodiment 19 G9 Polymkeric substance 9 13 14 1500
Embodiment 20 G10 Polymkeric substance 10 13 13 1550
Comparative example 7 G11 D-1 20 85 1250
Comparative example 8 G12 D-2 18 150 1150
Comparative example 9 G13 D-3 More than 1200 Gelation 1000
Comparative example 10 G14 D-4 15 70 1250
Comparative example 11 G15 D-5 15 75 1250
Comparative example 12 G16 D-6 15 65 1250
[table 3]
The blue pigments dispersive composition Pigment dispersing agent Viscosity after just having disperseed (mPas) Viscosity after 1 week (mPas) Contrast gradient
Embodiment 21 B1 Polymkeric substance 1 16 16 1100
Embodiment 22 B2 Polymkeric substance 2 12 13 1150
Embodiment 23 B3 Polymkeric substance 3 11 11 1200
Embodiment 24 B4 Polymkeric substance 4 12 12 1200
Embodiment 25 B5 Polymkeric substance 5 12 13 1200
Embodiment 26 B6 Polymkeric substance 6 12 13 1200
Embodiment 27 B7 Polymkeric substance 7 12 14 1100
Embodiment 28 B8 Polymkeric substance 8 12 13 1150
Embodiment 29 B9 Polymkeric substance 9 13 14 1150
Embodiment 30 B10 Polymkeric substance 10 13 13 1150
Comparative example 13 B11 D-1 125 360 950
Comparative example 14 B12 D-2 225 490 900
Comparative example 15 B13 D-3 900 Gelation 700
Comparative example 16 B14 D-4 250 500 850
Comparative example 17 B15 D-5 300 720 800
Comparative example 18 B16 D-6 270 900 850
Shown in table 1～table 3 as can be known, be the pigment dispensing composition of the embodiment of polymkeric substance 1～10 for having used specific pigment dispersion agent of the present invention, the viscosity of composition is all lower, and the dispersiveness of pigment, dispersion stabilization excellence, the tunicle that is made by this pigment dispensing composition has obtained high-contrast.By inference, the tunicle that is made by pigment dispensing composition of the present invention has realized that high-contrast is to disperse equably because of the state of pigment particles with miniaturization.
On the other hand, used the pigment dispensing composition of the comparative example of the known pigment dispersing agent outside the scope of the present invention to have higher viscosity, compare with pigment dispensing composition of the present invention, the dispersiveness of pigment is lower, dispersion stabilization is also relatively poor, and the tunicle that uses this pigment dispensing composition to obtain can not obtain sufficient contrast gradient.
[embodiment 31]
The modulation of＜Photocurable composition 〉
In the pigment dispensing composition that contains red pigment (R1) that in embodiment 1, makes, further add each composition of putting down in writing in the following composition (4), mix, modulation contains the Photocurable composition of the present invention (colored resist liquid) of red pigment.
(forming (4))
80 parts of dipentaerythritol acrylates
(optical polymerism compound)
4-[o-bromo-p-N, N-two (ethoxy carbonyl) aminophenyl]-2,30 parts of 6-two (trichloromethyl)-S-triazine
(Photoepolymerizationinitiater initiater)
Benzyl methacrylate/methacrylic acid (=70/30) [mass ratio] multipolymer (weight-average molecular weight: 300 parts of 2-acetoxyl groups 10,000)-1-methoxy propane solution (solids component 30%)
(alkali soluble resins)
390 parts of 2-acetoxyl groups-1-methoxy propane (solvent)
＜used the making of the colour filter of Photocurable composition 〉
The Photocurable composition (colored resist liquid) that makes is coated on the glass substrate (1737 of 100mm * 100mm, CORNING company system) on, so that reach 0.650 as the x value of the index of depth of shade, dry 60 seconds (prebake conditions) in 90 ℃ baking oven.Then, to the whole surface of filming with 200mJ/cm 2(illumination 20mW/cm 2) expose, with filming with 1% aqueous solution covering of alkaline-based developer CDK-1 (FUJI FILM Electronic Materials Co., Ltd. system) after the exposure, left standstill 60 seconds.After leaving standstill, spray pure water with the shower shape and take wash-out developer.Then, with implemented in the manner described above exposure and develop after the heat treated 1 hour (rear baking) in 220 ℃ baking oven of filming, thereby form colour filter with colored pattern (pigmentary resin tunicle) at glass substrate, make painted filter substrate (colour filter).
The evaluation of＜colour filter 〉
The painted filter substrate (colour filter) that makes is estimated in the following way.The result as described in Table 4.
(3) contrast gradient
Place polaroid to clamp the pigmentary resin tunicle at the pigmentary resin tunicle of painted filter substrate, the BM-5 that makes with TOPCON company measures the brightness of polaroid when parallel and the brightness when vertical, the brightness when parallel when vertical brightness and the value that obtains (brightness during=brightness when parallel/vertical) as the index for the evaluation contrast gradient.It is higher to be worth larger expression contrast gradient.
(4) development
The zone (unexposed portion) that does not shine with light in the observation by light microscope exposure process has or not residue, thereby estimates development.
Zero: at unexposed portion, confirm not have fully residue.
△: at unexposed portion, confirm to have a little a little residue, but be no problem degree on using.
*: at unexposed portion, confirm obviously to have residue.
[embodiment 32～40]
Pigment dispensing composition among the embodiment 31 (R1) is used in the pigment dispensing composition (R2)～(R10) that makes among the embodiment 2～10 replaces, in addition all with embodiment 31 light modulated solidification compound (colored resist liquid) in the same manner.Make painted filter substrate (colour filter) with this colored resist liquid, carry out the evaluation same with embodiment 31.The result as described in Table 4.
[embodiment 41]
In the pigment dispensing composition that in embodiment 11, makes (G1), further add each composition of putting down in writing in the following composition (5), mix, modulation contains the Photocurable composition of the present invention (colored resist liquid) of veridian.
(forming (5))
50 parts of dipentaerythritol acrylates
(optical polymerism compound)
4-[o-bromo-p-N, N-two (ethoxy carbonyl) aminophenyl]-2,20 parts of 6-two (trichloromethyl)-S-triazine
(Photoepolymerizationinitiater initiater)
Benzyl methacrylate/methacrylic acid (=70/30[mass ratio]) multipolymer (weight-average molecular weight: 70 parts of 2-acetoxyl groups 10,000)-1-methoxy propane solution (solids component 30%)
(alkali soluble resins)
160 parts of 2-acetoxyl groups-1-methoxy propane (solvent)
＜used making and the evaluation of the colour filter of Photocurable composition 〉
The Photocurable composition (colored resist liquid) that makes is coated on the glass substrate (1737 of 100mm * 100mm, CORNING company system) on, make the y value as the index of depth of shade reach 0.600, dry 60 seconds (prebake conditions) in 90 ℃ baking oven.Then, to the whole surface of filming with 200mJ/cm 2(illumination 20mW/cm 2) expose, with filming with 1% aqueous solution covering of alkaline-based developer CDK-1 (FUJI FILM Electronic Materials Co., Ltd. system) after the exposure, left standstill 60 seconds.After leaving standstill, spray pure water with the shower shape and take wash-out developer.Then, with implemented in the manner described above exposure and develop after the heat treated 1 hour (rear baking) in 220 ℃ baking oven of filming, form colour filter on the glass substrate with colored pattern (pigmentary resin tunicle), make painted filter substrate (colour filter).
The mensuration of the contrast gradient of the painted filter substrate that makes and evaluation and the embodiment 31 of development are similarly carried out.The result as described in Table 5.
[embodiment 42～50]
Pigment dispensing composition among the embodiment 41 (G1) is replaced with the pigment dispensing composition that makes among the embodiment 12～20 (G2)～(G10), in addition all with embodiment 41 light modulated solidification compound (colored resist liquid) in the same manner.Make painted filter substrate (colour filter) with this colored resist liquid, similarly estimate with embodiment 31.The result as described in Table 5.
[embodiment 51]
In the pigment dispensing composition that in embodiment 21, makes (B1), further add each composition of putting down in writing in the following composition (6), mix, thereby modulation contains the Photocurable composition of the present invention (colored resist liquid) of blue pigments.
(forming (6))
150 parts of dipentaerythritol acrylates
(optical polymerism compound)
4-[o-bromo-p-N, N-two (ethoxy carbonyl) aminophenyl]-2,0 part of 6-two (trichloromethyl)-S-triazin-6
(Photoepolymerizationinitiater initiater)
Benzyl methacrylate/methacrylic acid (=70/30[mass ratio]) multipolymer (weight-average molecular weight: 600 parts of 2-acetoxyl groups 10,000)-1-methoxy propane solution (solids component 30%)
(alkali soluble resins)
1240 parts of 2-acetoxyl groups-1-methoxy propane (solvent)
＜used making and the evaluation of the colour filter of Photocurable composition 〉
The Photocurable composition (colored resist liquid) of modulation is coated on the glass substrate (1737 of 100mm * 100mm, CORNING company system) on, so that reach 0.090 as the y value of the index of depth of shade, dry 60 seconds (prebake conditions) in 90 ℃ baking oven.Then, to the whole surface of filming with 200mJ/cm 2(illumination 20mW/cm 2) expose, with filming with 1% aqueous solution covering of alkaline-based developer CDK-1 (FUJI FILM Electronic Materials Co., Ltd. system) after the exposure, left standstill 60 seconds.After leaving standstill, spray pure water with the shower shape and take wash-out developer.Then, with implemented in the manner described above exposure and develop after the heat treated 1 hour (rear baking) in 220 ℃ baking oven of filming, thereby form colour filter with colored pattern (pigmentary resin tunicle) at glass substrate, make painted filter substrate (colour filter).
The mensuration of the contrast gradient of the painted filter substrate that makes and evaluation and the embodiment 31 of development are similarly carried out.The result as described in Table 6.
[embodiment 52～60]
Pigment dispensing composition among the embodiment 51 (B1) is replaced with the pigment dispensing composition that makes among the embodiment 22～30 (B2)～(B10), in addition all with embodiment 51 light modulated solidification compound (colored resist liquid) in the same manner.Make painted filter substrate (colour filter) with this colored resist liquid, carry out the evaluation same with embodiment 31.The result as described in Table 6.
[comparative example 19～24]
The pigment dispensing composition (R1) that is made by embodiment 1 among the embodiment 31 is replaced with the pigment dispensing composition that makes in the comparative example 1～6 (R11)～(R16), in addition all with embodiment 31 light modulated solidification compound (colored resist liquid) in the same manner.Make painted filter substrate (colour filter) with this colored resist liquid, carry out the evaluation same with embodiment 31.The result as described in Table 4.
[comparative example 25～30]
The dispersible pigment dispersion (G1) that is made by embodiment 11 among the embodiment 41 is replaced with the pigment dispensing composition that makes in the comparative example 7～12 (G11)～(G16), in addition all with embodiment 41 light modulated solidification compound (colored resist liquid) in the same manner.Make painted filter substrate (colour filter) with this colored resist liquid, carry out the evaluation same with embodiment 41.The result as described in Table 5.
[comparative example 31～36]
The dispersible pigment dispersion (B1) that is made by embodiment 21 among the embodiment 51 is replaced with the dispersible pigment dispersion that makes in the comparative example 13～18 (B11)～(B16), in addition all with embodiment 51 light modulated solidification compound (colored resist liquid) in the same manner.Make painted filter substrate (colour filter) with this colored resist liquid, carry out the evaluation same with embodiment 51.The result as described in Table 6.
[table 4]
The red pigment dispersive composition Contrast gradient Development
Embodiment 31 R1 1150 ○
Embodiment 32 R2 1300 ○
Embodiment 33 R3 1300 ○
Embodiment 34 R4 1300 ○
Embodiment 35 R5 1300 ○
Embodiment 36 R6 1300 ○
Embodiment 37 R7 1250 ○
Embodiment 38 R8 1300 ○
Embodiment 39 R9 1300 ○
Embodiment 40 R10 1300 △
Comparative example 19 R11 1050 ×
Comparative example 20 R12 900 ×
Comparative example 21 R13 850 △
Comparative example 22 R14 1050 ×
Comparative example 23 R15 1050 ×
Comparative example 24 R16 1050 ×
[table 5]
The veridian dispersive composition Contrast gradient Development
Embodiment 41 G1 1400 ○
Embodiment 42 G2 1450 ○
Embodiment 43 G3 1500 ○
Embodiment 44 G4 1500 ○
Embodiment 45 G5 1450 ○
Embodiment 46 G6 1450 ○
Embodiment 47 G7 1400 △
Embodiment 48 G8 1450 ○
Embodiment 49 G9 1400 ○
Embodiment 50 G10 1500 △
Comparative example 25 G11 1200 ×
Comparative example 26 G12 1000 ×
Comparative example 27 G13 950 ×
Comparative example 28 G14 1150 ×
Comparative example 29 G15 1150 ×
Comparative example 30 G16 1150 ×
[table 6]
The blue pigments dispersive composition Contrast gradient Development
Embodiment 51 B1 1050 ○
Embodiment 52 B2 1050 ○
Embodiment 53 B3 1150 ○
Embodiment 54 B4 1100 ○
Embodiment 55 B5 1100 ○
Embodiment 56 B6 1100 ○
Embodiment 57 B7 1000 ○
Embodiment 58 B8 1050 ○
Embodiment 59 B9 1050 ○
Embodiment 60 B10 1100 △
Comparative example 31 B11 900 △
Comparative example 32 B12 800 ×
Comparative example 33 B13 700 △
Comparative example 34 B14 750 △
Comparative example 35 B15 750 △
Comparative example 36 B16 750 △
Shown in table 4～6, use the painted filter substrate (colour filter of embodiment) of the Photocurable composition manufacturing of the embodiment that contains pigment dispensing composition of the present invention and obtain all to obtain high-contrast, demonstrate good development.And the poor contrast of the painted filter substrate of comparative example, and sufficient development property.

Claims (11)

1. pigment dispensing composition, it contains pigment and polymkeric substance and forms in organic solvent, and described polymkeric substance comprises the copolymerization units that comes from following monomer M-2, M-3, M-4, M-5, M-6, M-7, M-10, M-11 or M-13,
2. pigment dispensing composition according to claim 1, wherein, described polymkeric substance is the graft copolymer that further comprises the copolymerization units that comes from the polymerizability low-grade polymer that has endways ethylenic unsaturated bond.
3. pigment dispensing composition according to claim 1, wherein, described polymkeric substance is the polymkeric substance that further comprises the copolymerization units that comes from the monomer with acidic group.
4. pigment dispensing composition according to claim 1, wherein, the acid number of described polymkeric substance is 10～150mgKOH/g.
5. pigment dispensing composition according to claim 1, wherein, described pigment is from C.I. pigment yellow 13 9, C.I. Pigment Yellow 73 150, C.I. pigment green 36, C.I. Pigment red 177, C.I. Pigment red 254, C.I. pigment Blue 15: 6 and the group that forms of C.I. pigment Violet 23 at least a pigment selected.
6. Photocurable composition, it contains: pigment dispensing composition claimed in claim 1, optical polymerism compound and Photoepolymerizationinitiater initiater.
7. Photocurable composition according to claim 6, it further contains alkali soluble resins.
8. according to claim 6 or 7 described Photocurable compositions, wherein, described Photoepolymerizationinitiater initiater is at least a Photoepolymerizationinitiater initiater of selecting from triazine based compound, the lophine group that namely 2,4,5-triphenyl imidazole dimer class based compound and oxime compound form.
9. according to claim 6 or 7 described Photocurable compositions, it is used for colour filter.
10. colour filter, it has the colored pattern that right to use requires 9 described Photocurable compositions to form at substrate.
11. the manufacture method of colour filter, it comprises following operation: photosensitive film forms operation, and it is Photocurable composition claimed in claim 9 to be applied directly on the substrate or across other layer be applied on the substrate, thereby forms photosensitive film; Colored pattern forms operation, and it is by formed photosensitive film being carried out successively pattern exposure and develop to form colored pattern.
CN2007101483983A 2006-09-01 2007-08-31 Pigment dispensing composition, optical solidified composition, color filter and manufacturing method thereof Expired - Fee Related CN101134800B (en)

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